Transition metal complexes of substituted 2 -benzimidazolecarbamic acid,alkyl esters and their preparation

ABSTRACT

AND X; R1, R2, R3, R4, Z, N AND ME ARE AS DEFINED HEREINAFTER. AN EXEMPLARY SPECIES OF THE GENERAL CLASS IS THE COMPLEX: 1-(BUTYLCARBAMOYL)-2-BENZIMIDAZOLECARBAMIC ACID, METHYL ESTER 2:1 MANGANESE COMPLEX.   Q IS -CO-NH-R2, -CO-R3, -CDER4 OR -S-Z   Q IS   1-Q,2-((-)C(-O-R1)=N-),X-BENZIMIDAZOLE.(H2O)N ME(+2)   TRNASITION METAL COMPLEXES OF SUBSTITUTED 2-BENZIMIDAZOLECARBAMIC ACID, ALKYL ESTERS OF THE FOLLOWING FORMULA ARE USEFUL AS MITE OVICIDES AND FUNGICIDES:

United States Patent Ofi 3,562,282 Patented Feb. 9, 1971 US. Cl. 260-29913 Claims ABSTRACT OF THE DISCLOSURE Transition metal complexes ofsubstituted Z-benzimidazolecarbamic acid, alkyl esters of the followingformula are useful as mite ovicides and fungicides:

C-OR1 ID N and X, R R R R Z, n and Me are as defined hereinafter.

where Qis An exemplary species of the general class is the complex: 1(butylcarbamoyl) 2 benzimidazolecarbamic acid, methyl ester 2:1manganese complex.

CROSS REFERENCE TO RELATED APPLICATIONS This application is acontinuation-in-part of my copending application Ser. No. 721,061, filedApr. 12, 1968 now abandoned, which application is a continuation-in-partof my copending application Ser. No. 629,900 filed Apr. 11, 1967 nowabandoned, which application is a continuationin-part of my copendingapplication Ser. No. 548,034, filed May 6, 1966.

BACKGROUND OF THE INVENTION This invention relates to the novelcomplexes formed between transition metal cations and substitutedZ-aminobenzimidazoles and to methods of using these complexes to preventor mitigate damage to plants and inanimate organic materials by fungiand mites. The invention also relates to processes for preparing suchcomplexes.

The survival of man has for a long time been dependent in a largemeasure upon his ability to protect from the various agents ofdestruction, plants and their products which satisfy his basic needs.With the rapidly increasing population of the world it becomesimperative that there be continuing great improvements in the efiiciencyof the materials and the methods employed to provide this protection.These improvements can be in the form of effective control of more kindsof pests or in the form of requiring less material or work. Thematerials and methods of this 5 invention represent marked advances inboth of these possible areas of improvement, as will be explained morefully.

I have discovered that application of the complexes of this invention bythe methods of this invention, surprisingly, entirely precludes orreduces damage to plants and inanimate organic materials due to bothfungi and mites. Fungus mycelia are killed or prevented from developingfurther by the presence of one or more of the complexes, i.e., thecomplexes are fungicidal or fungistatic. The complexes further preventmite populations from expanding or reduce them to a low level or eveneliminate them by preventing the normal hatching of their eggs, i.e.,the complexes are mite ovicides.

The complexes and methods of this invention also make possible thecontrol of damage by both fungi and mites with an amazingly small amountof chemical and with surprisingly little effort. These advantages aredue in large measure to the fact that the complexes when properlyapplied, can enter and move about in plants. This means that an entireplant can be protected from mites and fungi with a simple application ofthe chemical to only a part of it, i.e. the complexes are systemic.Further, if the complexes are applied after a disease-causing fungus isalready established within a plant, they can enter the tissues anderadicate the infection, i.e. the complexes are curative. Thus, the needfor applications prior to the actual incidence of the disease iseliminated under many circumstances.

SUMMARY OF THE INVENTION It has been found that the above outstandingfungicidal and mite ovicidal activity can be obtained by applying to thelocus of mite or fungus infestation, the complexes represented by thefollowing formula:

Formula I wherein Q is R; is alkyl of 1 through 12 carbon atoms; alkylof 1 through 12 carbon atoms substituted with cyano, hydroxy, -ORchlorine or bromine; alkenyl of 3 through carbon atoms; alkynyl of 3through 10 carbon atoms;

cycloalkyl of 3 through 8 carbon atoms; (cycloalkyl) alkyl of 7 through10 carbon atoms;

X; or X 3 Z is alkyl of 1 through 3 carbon atoms; alkyl of 1 through 3carbon atoms substituted with chlorine; phenyl; phenyl substituted withnitro, chlorine or methyl; benzyl; or benzyl substituted with nitro,chlorine or methyl;

D and E are oxygen or sulfur, provided that one must be sulfur;

Me is zinc, copper, nickel, manganese, cobalt, cadmium,

iron or chrominum; and

n is 0, /2,1,1 /2, 2, or 3.

Preferred within Formula I because of their greater pesticidal activityare the compounds of the following formula:

Formula II wherein Q1 is NHR2' or -so01 R is methyl or ethyl; R is alkylof 1 through 8 carbon atoms; Me is zinc or manganese; and n is O,1,l /2or 2.

Most preferred within Formula I because of their activity are thefollowing complexes: l-(butylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex and1-(butylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 manganese complex.

The invention is also directed to novel processes for preparing thecomplexes of Formula I. In these processes, the startingbenzimidazolecarbamate is reacted with the appropriate metal salt in asystem composed of (a) an aqueous solution of the metal salt, (b) asuitable organic solvent, and (c) the benzimidazolecarbamatc whichinitially is present mostly in undissolved solid form in the organicsolvent and (d) where necessary, an aqueous solution of a base. Thesystem is agitated vigorously and after 4 a suitable period of time, theproduct complex is separated by pouring the mixture into water followedby filtration, or by direct filtration of the reaction mixture,depending upon the type of reaction employed.

DETAILED DESCRIPTION OF THE INVENTION The novel complexes of theinvention are made by reacting a benzimidazolecarbamate With theappropriate metal salt. The benzimidazolecarbamate reactants used are ofthe general formula:

X is hydrogen, halogen, alkyl of 1 through 4 carbon atoms, nitro, oralkoxy of 1 through 4 carbon atoms;

R is methyl, ethyl, isopropyl or sec-butyl;

R is alkyl of 1 through 12 carbon atoms; alkenyl of 3 through 12 carbonatoms; alkynyl of 3 through 12 carbon atoms; cycloalkenyl of 4 through 8carbon atoms; cycloalkyl of 3 through 8 carbon atoms; cycloalkyl of 3through 8 carbon atoms substituted with methyl, methoxy, or chlorine;(cycloalkyl)-alkyl of 7 or 8 carbon atoms; phenyl; phenyl substitutedwith methyl, ethyl, methoxy, ethoxy, nitro, CF CH SO or halogen; benzyl;benzyl substituted with methyl, nitro, methoxy, or halogen or hydrogen;

R is hydrogen; alkyl of 1 through 12 carbon atoms; alkyl of 1 through 12carbon atoms substituted with cyano, OR acetoxy, chlorine, or fluorine;alkenyl of 3 through 10 carbon atoms; alkynyl of 3 through 10 carbonatoms; cycloalkyl of 3 through 8 carbon atoms; or

R is alkyl of 1 through 12 carbon atoms; alkyl of 1 through 12 carbonatoms are substituted with cyano, hydroxy, OR chlorine or bromine;alkenyl of 3 through 10 carbon atoms; alkynyl of 3 through 10 carbonatoms; cycloalkyl of 3 through 8 carbon atoms; (cycloalkyl)alkyl of 7through 10 carbon atoms;

Z is alkyl of 1 through 3 carbon atoms; alkyl of 1 through 3 carbonatoms substituted with chlorine; phenyl; phenyl substituted with nitro,chlorine or methyl; benzyl; or benzyl substituted with nitro, chlorineor methyl; and

D and E are oxygen or sulfur, provided that one must be sulfur.

Among the benzimidazolecarbamates, the compounds where X is hydrogen Qis R is methyl or ethyl; and

R is alkyl of 1 through 8 carbon atoms are preferred in view of the highactivity of the product complex.

Most preferred on the basis of highest activity of the resulting complexare the following compounds: 1-butylcarbamoyl-2-benzimidazolecarbamicacid, methyl ester The benzimidazolecarbamate reactants can be preparedas described in the art, for example in Belgian Patent 698,071.

Thus, they can be prepared by reacting a 2-benzimidazolecarbamate of theformula:

H C-N-COOR with one equivalent of an alkyl chlorothiolformate, alkylchlorothionoformate, alkyl chlorodithioformate, isocyanate, acylchloride or a sulfenyl chloride in an inert solvent. TheZ-benzimidazolecarbamate can be prepared as taught in US. Pat.3,010,768.

The transition metal salts used in preparing the metal complexes of thisinvention are salts of zinc, manganese, nickel, cobalt, copper, cadmium,iron and chromium. The salts may be acetates, chlorides, sulfates,nitrates, citrates and the like. Preferred for reasons of highfungicidal activity are complexes containing zinc and manganese.

In some cases, the complexes may have different structures, e.g., theymay be 1:1 complexes rather than 2:1 complexes, and they may containanions such as acetate ions if the complex was made from a metalacetate, etc. However, such complexes are usually obtained by methodsother than the novel methods of this invention. For example, they may beobtained by reacting the benzimidazole derivative and the metal salt inan organic solvent such as ethyl acetate in the absence of water. Theproducts thus obtained have the disadvantage of being unstable in thepresence of water and are therefore not preferred.

The novel complexes of the present invention may be prepared either byknown methods or by the novel processes of this invention. In a knownpreparation such as described in Example 6, the benzimidazolecarbamatederivative is dissolved in a suitable solvent such as dimethylformamide,and a molar equivalent of sodium methoxide is added in order to convertthe benzimidazolecarbamate to its sodium derivative. To the solutionthus obtained, one half molar equivalent of the desired metal salt isadded in the form of a solution in dimethylformamide. After stirring fora suitable period, for example l minutes, the reaction mixture is pouredinto a mixture of ice and water with stirring, and the product isisolated by filtration, washing and drying.

In contrast to this known process, one of the novel processes of thisinvention permits slurrying rather than dissolving thebenzimidazolecarbamate as well as the heavy metal salt indimethylformamide, thus drastically reducing the amount ofdimethylformamide required. Furthermore, the novel process usesconcentrated aqueous sodium or potassium hydroxide or carbonate insteadof the much more costly sodium methoxide, or can use tertiary (loweralkyl) amines or tetra (lower alkyl) ammonium hydroxides, andfurthermore, may use the cheaper metal salts of inorganic acids, egsulfates, chlorides, or nitrates, instead of the much more expensivesalts of organic acids, e.g. acetic acid; see Example 10.

In different embodiments of this novel process, the dimethylformamideused as the solvent is replaced by acetone (Example 11) or methyl ethylketone (Example 12) and the heavy metal salt is added in the form of ahighly concentrated or saturated aqueous solution. The use of methylethyl ketone has the advantage that the metal complex can be isolated bysimple filtration without the necessity of pouring the reaction mixtureinto water. The methyl ethyl ketone recovered from the filtration can beused as such in preparing the next batch of metal complex. It will beclear to one skilled in the art that these processes, particularly theone employing methyl ethyl ketone, can be operated in a continuousmanner.

In another novel process according to the present invention, thebenzimidazolecarbamate is reacted with the metal salt in a three-phasesystem consisting of an aqueous solution of the metal salt, a suitablewater-immiscible organic solvent such as ethyl acetate, and thebenzimidazolecarbamate which is present mostly in undissolved solid formin the organic solvent. This process obviates the use of a base. Thethree-phase system is agitated vigorously, and after a suitable periodof stirring which depends upon the reaction conditions used, the solidphase has passed from the organic phase to the aqueous phase, whichsignifies that the reaction is complete. This phenomenon can be checkedby stopping agitation for a moment in order to allow the liquid phasesto separate. The product is separated by filtration or similar means,and the two liquid phases in the filtrate can be used directly inpreparing the next batch of product. It will be clear to one skilled inthe art that this novel process is eminently suitable for continuousoperation, e.g. in a pipe reactor.

In describing this process of this invention in greater detail, Example1 below can be used as a starting point. In this example, an essentiallysaturated solution of 6 molar equivalents of zinc acetate dihydrate inwater is mixed with about a 10% (by weight) slurry of one molarequivalent of 1 (butylcarbamoyl) 2 benzimidazolecarbamic acid, methylester in ethyl acetate, at room temperature. The volumes of the twoliquid phases are equal and are each about 3200 cc. per mole of thebenzimidazolecarbamate. Under these conditions, assuming vigorous andefiicient agitation so that the stirred reaction mixture has theappearance of an emulsion, the conversion to the metal complex isvirtually instantaneous. Thus, these or similar conditions areparticularly suitable for a continuous process, e.g. in a pipe reactor.

On stopping agitation, the two liquid phases separate virtuallyimmediately. The two phases may first be separated, followed byfiltration of the aqueous phase in order to obtain the product, or thethree-phase system may be filtered as such without prior separation. Ineither case, the two-phase filtrate may be used as such for preparingthe next batch of metal complexes by simply adding the required amountsof benzimidazolecarbamate and metal salt.

The conditions described in Example 1 can be varied within wide limits.For example, the amount of Zinc acetate dissolved in the aqueous phasecan be reduced from 6 molar equivalents to 1 molar equivalent (which isexcess over theoretical). At this concentration of zinc acetate, theconversion to the metal complex is not instantaneous but still veryrapid. However, if the amount of zinc acetate is cut down still further,for example to 10% excess over theoretical, the other conditionsremaining the same, the conversion proceeds so slowly that it is stillincomplete after 6 hours of agitation with a normal laboratory stirrer.It should be noted here that the use of specially designed high-speedagitators, Waring Blendors, etc. would of course tend to reduce theperiod required for complete conversion.

The concentration of the zinc acetate in the aqueous phase can be belowthe saturated level. For example, when using 1 molar equivalent of zincacetate, as above (100% excess), in twice the amount of water (about6400 cc. per mole of benzimidazolecarbamate) the conversion still takesplace, but the time required is 1-2 hours.

The volumes of water and ethyl acetate used may both be reduced as wellas increased. However, the volumes should preferably not be reducedbelow the point where 7 efficient mixing of the phases is hampered.Increasing these volumes lengthens the reaction period and generallyoffers no great advantages.

Water and ethyl acetate must both be present, however. As discussedabove, the use of ethyl acetate alone results in the formation of a 1:1zinc acetate complex which is unstable in water and therefore notpreferred. The use of water alone, even for prolonged reaction periods,does not result in any noteworthy conversion. The ethyl acetate may bereplaced by other suitable water immiscible esters and ethers (e.g. amylacetate, diethyl ether), but the use of hydrocarbons, chlorinatedhydrocarbons, etc. (e.g. benzene, hexane, chloroform) generally resultsin poor or slow conversions and the latter solvents are therefore notpreferred. The use of watermiscible ethers such as tetrahydrofuran leadsto the formation of rather intractable mixtures which, although notdevoid of fungitoxicity, are not preferred.

As discussed above, ethyl acetate may also be replaced by suchwater-miscible or partly water-miscible solvents as dimethylformamide,acetone or methyl ethyl ketone, but in these cases the presence of abase is necessary for obtaining high yields, and the heavy metalsulfates, for example, work just as well as the acetates.

Referring now to the process of Example 1, the pH of the reactionmixture plays a part in the ease and degree of conversion as evidencedby the fact that with zinc chloride, the conversion proceeds with muchless case than with zinc acetate. It is advisable, for eachbenzimidazolecarbamate and for each metal salt, to determine theconditions of optimum pH and, if necessary, to adjust and maintain thepH at the optimum level.

With reference to all novel processes of this invention, it can bestated that the temperature at which the conversion is carried out canin general vary between the freezing point and the boiling point of thereaction mixture. Elevated temperatures can, for example, beadvantageous in cases where the metal salt used has lowwater-solubility. However, the l-substituted benzimidazolecarbamic acidesters used as starting meterials in this invention show varying degreesof thermal instability at elevated temperatures depending upon thenature of the substituent in the 1-position. Thus, in cases where thisthermal instability is pronounced, it is recommended that the otherreaction conditions are so chosen that the conversion requires a minimumof time, and that the temperature be kept below, say, 50 C. It ispreferred to carry out the reactions at room temperature withoutexternal heating or cooling. In some cases, depending upon thesolubility of the product in the organic solvent, it is of someadvantage in regard to the yield to cool the reaction mixture to, say -3C. before filtering.

Another factor which influences ease of reaction and yield is theparticle size of the organic starting material. [For example, it wasfound that micropulverization of the starting material can in some casesincrease the yield of metal complex by as much as under otherwiseidentical conditions.

The novel complexes of this invention as prepared by the known and novelprocesses discussed above are usually obtained in the form of dihydratesunder ordinary drying conditions, such as for example spreading out inthe air or drying in a vacuum oven at slightly elevated temperatures,e.g., up to 50 C. However, the materials may be converted to formscontaining less water, for example the corresponding monohydrates,hemihydrates or even the completely anhydrous forms. The monohydratesand anhydrous forms are by far the most frequently obtained forms.

They are obtained for example by vacuum drying at more elevatedtemperatures, eg 60100 C., or by drying in solution or suspension. Thesemethods are illustrated in Examples 13-16. In some cases, conversion ofthe dihydrates to the corresponding monohydrates or anhydrous formsresults not only in increased antifungal and mite ovicidal activity butalso in markedly increased storage stability.

This is particularly true in the case of the l-carbamoyl compounds ofthis invention. As discussed, in Examples 1316, that drying of thedihydrates of this type to the corresponding monohydrates or anhydrousforms results in changes in the IR spectra (e.g. the appearance of apeak at 5.8 1.) which, together with the increased stability, point to astructural rearrangement in the metal complex whereby the --COOR groupin the 2-position no longer participates directly in the bonding of themetal atoms and this bonding function is taken over by the carbamoylgroup in the 1-position. Thus, it should be kept in mind that theappropriate compounds of Formula I or II in which n=0, /2 or 1 may havestructures such as:

C -N CooRi H However, for purposes of convenience we shall continue torefer to the compounds of this invention as compounds of Formula I orII.

The following examples illustrate the preparation of the compounds ofFormula I. The amounts given are in parts by weight unless otherwisespecified. In some of the examples both parts (by weight) and parts byvolume are mentioned; in these cases, the units of measure correspond inthe form of grams to milliliters, kilograms to liters, etc.

Example 1.-Preparation of 1- (butylcarbamoyl) -2-benzimidazolecarbamicacid, methyl ester 2:1 zinc complex, dihydrate To a virtually saturatedsolution of 66 parts of zinc acetate dihydrate in 160 parts of water isadded 14.5 parts of 1 (butylcarbamoyl)-2-benzimidazolecarbamic acid,methyl ester and 144 parts (160 parts by volume) of ethyl acetate. Thismixture contains 6 moles of zinc acetate dihydrate per mole of organicstarting material. It is a three-phase system in which the solid organicstarting material is present in the ethyl acetate layer in mostlyundissolved form. The mixture is agitated vigorously at roomtemperature. After a few minutes, the stirrer is stopped and the mixtureis allowed to separate into its phases. It is observed that the solidmaterial is now present in the aqueous layer, signifying that theconversion is complete. Under the conditions of this ex ample, theconversion is virtually instantaneous. The reaction mixture is cooled to05 C. in order to increase the yield, filtered, and the solid is washedwith cold ethyl acetate and cold water, and dried. The product weighs15.3 parts The ethyl acetate layer is found to con tain, on evaporation,1 part of organic starting material, so that the yield is 97% based onthe starting material converted.

The IR spectrum shows the following characteristic changes as comparedwith the IR spectrum of the organic starting material: thecharacteristic peaks shown by the etc.

parent compound at about 5.8 and 8.8a have disappeared, and new peakshave appeared at about 6.0, 6.6 and 8.7a.

NMR spectrum.The product has a triplet at .88'r with a coupling constantJ=5.1 cps. This absorption is due to .the proton attached to N in thel-butylcarbamoyl group. This same triplet is present in the parentcompound and occurs at .45T with a coupling constant of J=5.1 cps.

The presence in the product of the essentially unchanged absorption ofthe proton attached to N in the l-butylcarbamoyl group constitutesstrong evidence for the lack of involvement of the butylcarbamoyl moietyof the molecule with the metal atom.

The spectrum of the parent compound shows absorption at 2.287' (broad)assigned to the proton attached to nitrogen in the 2-position. In theproduct, this peak is no longer present, indicating that this proton hasbeen replaced by the metal.

Rapid exchange of the two protons discussed above is hindered indeuterodimethylsulfoxide (used as the solvent), thus allowingobservation of their separate absorption positions and, whereapplicable, their coupling constants.

There is no other absorption below 1.5-r in either the product or theparent compound. Changes in the absorption patterns of the aromatichydrogens support the assignment of the association of .the 3-nitrogenwith the metal.

Elemental analysis.Calc. for C H N O Zn (percent): C, 49.5; H, 5.6; N,16.5; Zn, 9.6. Found (percent): C, 49.50; H, 5.61; N, 16.42; Zn, 9.59.

Melting pint.As is to be expected from a compound of this type, theproduct melts over a very broad range.

Dehydrati0n.As described in more detail in one of the followingexamples, the product loses two molecules of water upon heating in avacuum oven at 6065 C.

Structural f0rmulaiThe above information is consistent with thefollowing structural formula:

Example 2.Preparation of l-(butylcarbamoyl)-2-benzimidazolecarbamicacid, methyl ester 2:1 manganese complex, dihydrate CHaO-C To a solutionof 74 parts of manganese acetate tetrahydrate in 220 parts of water isadded 14.5 parts of 1- (butylcarbamoyl)-2-benzimidazolecarbamic acid,methyl ester and 171 parts (190 parts by volume) of ethyl acetate. Themixture is agitated vigorously at room temperature for two hours, and isthen filtered. The solid is washed with ethyl acetate and water, anddried. Spectral and elemental analyses of the type discussed in Example1 show that under the conditions used, the conversion is not complete,and that the material obtained is a mixture of about 55% manganese 2:1complex, dihydrate and about 45% parent compound. The parent compound isremoved by slurrying the material with chloroform, filtering and washingwith chloroform. The insoluble solid consists of the desired complex.

The IR spectrum shows the absence of peaks at 5.8 and 8.8a which arecharacteristic for the starting ma- 10 terial, and the presence of peaksat 6.0, 6.6 and 0.7 which are characteristic for the desired manganese2:1 complex, dihydrate.

Elemental analysis.Calc. for C H N O Mn (percent): C, 50.25; H, 5.7; N,16.8. Found (percent): C, 50.47;H, 5.75; N, 16.75.

The structural formula of this material is as shown in Example 1 withthe difference that a manganese atom replaces the zinc atom.

Example 3.Preparation of l-(butylcarbamoyl)-2-benzimidazolecarbamicacid, methyl ester 2:1 copper complex To a solution of 60 parts ofcupric acetate dihydrate in 850 parts of water is added 29 parts ofl-(butylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester and 405parts (450 parts by volume) of ethyl acetate. The mixture is stirredvigorously for 3 /2 hours at room temperature; it is then filtered. Thesolid is washed with ethyl acetate and water, and dried. It consists ofa light green powder and weighs 28 parts. The IR spectrum showscharacteristic peaks at 5.95, 6.5 and 8.7a. There are no peaks at 5.8and 88 Elemental analysis.-Calc. for C H N O Cu (percent): C, 52.45; H,5.4; N, 17.5. Found (percent): C,

Example 4.Preparation of l-(butylcarbamoyl)-2-benzimidazolecarbamicacid, methyl ester 2:1 nickel complex, trihydrate To a solution of 75parts of nickel acetate tetrahydrate in 220 parts of water is added 14.5parts of l-(butylcarbamoyl)-2-benzimidazolecarbamic acid, methyl esterand 171 parts of ethyl acetate. The mixture is stirred vigorously atroom temperature for 2 hours. It is then filtered, and the solid iswashed with ethyl acetate, water and acetone, and dried. It weighs 11parts.

The infrared spectrum indicates the presence of a small amount of parentmaterial and furthermore clearly shows the characteristic peaks of thedesired product at 6.0, 6.6 and 8.7,a. The product is a lightgreenish-blue powder.

Elemental analysis.-Calc. for a 9:1 mixture of product and parentmaterial (percent): C, 49.63; H, 5.84; N, 16.51. Found (percent): C,49.69; H, 5.80; N, 16.06.

Example 5.Preparation of 1-(butylcarbamoyl)-2-benzimidazolecarbamicacid, methyl ester 2:1 cobalt complex, dihydrate To a solution of 75parts of cobalt acetate tetrahydrate in 220 parts of water is added 14.5parts of 1- (butylcarbamoyl)-2-benzimidazolecarbarnic acid, methyl esterand 171 parts of ethyl acetate. The mixture is stirred vigorously atroom temperature for 2 hours. It is then filtered, washed with ethylacetate, water and acetone, and dried. The light pink powder weighs 16parts. The infrared spectrum shows characteristic peaks at 6.0, 6.6 and8.7 It also indicates the presence of a small amount of startingmaterial.

Elemental analysis.Calc. for a 9:1 mixture of product and parentmaterial (percent): C, 50.80; H, 5.76; N, 16.87; Co, 7.87. Found(percent): C, 50.89; H, 5.87; N, 16.62; Co, 7.56.

Example 6.Preparation of the manganese complex of Example 2 by a knownmethod 11 into 3000 parts of ice and water, while stirring. Afterstirring for another 30 minutes, the mixture is filtered, washed withwater and dried. The product is identical in all respects with theproduct of Example 2.

Example 7.Preparation of the product of Example 1 in diethylether andwater The preparation of Example 1 is repeated with this difference thatthe 160 parts by volume of ethyl acetate is replaced by an equal volumeof diethyl ether.

The reaction proceeds in essentially the same manner, and the product isidentical in all respects with that of Example 1.

'Example 8.-Preparation of the product of Example 1 in amyl acetate andwater The preparation of Example 1 is repeated with this difference thatthe 160 parts by volume of ethyl acetate is replaced by an equal volumeof n-amyl acetate. The reaction proceeds in essentially the same manner,and the product is identical in all respects with that of Example 1.

[Example 9 Using the method of Example 1, the organic materials listedin the following table are reacted With zinc acetate in water-ethylacetate in the same molar quantities as in Example 1 to give theproducts litscd.

10 Large drops of the aqueous phase are visible in the acetone phaseafter completion of the addition. Stirring is continued for three hours.Thus, the mixture is poured into 250 parts of water with stirring. Afterstirring for minutes, the suspension is filtered, and the solid is 15washed and dried. The product, which weighs 6.2 parts, is

identical in all respects with that of Example 2.

Example 12.Preparation of the product of Example 2 in methyl ethylketone and water in the presence of a base A slurry of 5.8 parts of1-(butylcarbamoyD-Z-benz- *imidazolccarbamic acid, methyl ester in partsby volume of methyl ethyl ketone is stirred vigorously, and

5 1.6 parts of 50% aqueous sodium hydroxide is added dropwise. Stirringis continued for 1 hour. To the suspension in methyl ethyl ketone of thesodium derivative TAB 11E Starting materiall-(n-hexylearbamoyl)-2-bcnziruidazolecarbamic acid, methyl ester1-(n-0ctylearbam0yl)-2-l enzimidazolccarbamic acid, methyl ester l-(A'-deeenylcarbamoyl)-2-benzimidazoleearbamic acid, methyl ester1'(allylcarbam0yl)-2 benzimidazolecarbamic acid, methyl esterl-(methylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester1-(cyclohexylcarbamoyl)-2-benzirni laz0lecarbamic acid, methyl ester1-(benzylcarbarnoyl)-2-benzimidazoleearbamie acid, methyl ester1-(p-methoxybenzylcarbamoyl) -2-benzimidazolecarbamic acid, methylester--. l-(p-methoxybenzylcarbamoyl) -2-benzimidazole1-(p-methoxyphenylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester-1-(p-methcxyphenylcarbamoyl) -2-benzimidazolel-(triehloromethylthio)-2-beuzimidazolecarbamic acid, methyl esterl-(methylthiocarbonyl) -2-benzimidazolecarbamic acid, metyl esterl-(methylcarbamoyl) -2-benzimidaz0lecarbamie acid, isopropyl esterl-(n-hexylcarbamoyl)-2-benzimidazolecarbamie e. l-(n-oetylearbamoyl)-2-henzimidazolecarbamic 1(allylc arbameyl) -2-benzimidazolecarbamie1-(methylcarbamoyl)-2-benzimidazolecarbamic hydrate.l-(cyclohexylcarbamoyl)-2-benzimidazolecarba1-(benzylearbamoyl)-2-benzimidazolecarbamie1-(trichleromethylthio)-2-benzi midazolecarbadr e.1(methylthi0carbcnyl)2-benzimidazoleearbal-(methylearbamoyl)2benzimidaz0lecarbamicInfrared spectrum, Characteristic peaks at 5.96, 6,55 and 8.7 a.

Product acid, methyl ester 2:1 zinc complex, monohydrat 5.93, 6.53 and8.7 a.

acid, methyl ester 2:1 zinc complex, dihydrate.

5.96, 6.55 and 8.72 p.

mict acid, methyl ester 2:1 zinc complex, dihy- 6.0, 6.5 and 8.63 [1.

acid, methyl ester 2: 1 zinc complex, dihydrate.

5.92, 6.5 and 8.7 [1.

acid, methyl ester 2:1 zine complex, sesqui- 5.95, 6.5 and 8.7 p.finictaeid, methyl ester 2:1 zinc complex, dihyra e 5.92, 6,5 and 8.7 n.acid, methyl ester 2:1 zinc complex, sesquihydrate.

5.98, 6.57 and 8.7 p. earbamic acid, methyl ester 2:1 zine complex,dihydrate.

5.95, 6.6 and 8.8 p. carbamic acid, methyl ester 2:1 zinc complex,dihydrate.

6.46 11. mictacid, methyl ester 2:1 zinc complex, dihy- 6.45, 6.6 and8.6 p. mic acid, methyl ester 2:1 zinc complex, monohydrate.

5.92, 6.55 and 8.7 ,u. zcid, isoprepyl ester 2:1 zinc complex, dihyra e.

1 New peak.

Example 10.-Preparation of the product of Example 2 in dimethylformamideand water in the presence of a base Example 11.-Preparation of theproduct of Example 2 in acetone and water in the presence of a base 70Example of l-(butylcarbamoyl) 2 benzimidazolecarbamic acid,

methyl ester thus obtained is added, with stirring, a solution of 1.7parts by weight of manganese sulfate monohydrate in three parts ofwater. The two liquid phases (containing the third, solid phase) areclearly visible. Stirring is continued for three hours. Then, themixture is cooled in ice while stirring and filtered. The solid iswashed with methyl ethyl ketone and water, and dried. The product, whichWeighs 6.2 parts, is identical in all respects with the product ofExample l3.-Preparation of l-(butylcarbamoyD-Z- benzimidazolecarbamicacid, methyl ester 2:1 zinc complex, monohydrate Ten parts of thedihydrate of Example 1 are mixed with 50 parts by volume of concentratedaqueous ammonia, and the mixture is stirred for two hours. The

mixture is filtered, and the solid is dried. It weighs 9 parts andanalyzes as follows:

Calc. for the 2:1 zinc complex, monohydrate (percent): C, 50.8; H, 5.5;N, 16.95; Zn, 9.85. Found (percent): C, 50.41; H, 5.34; N, 17.74; Zn,9.96.

The infrared spectrum of the monohydrate product differs from that ofthe dihydrate mainly in that it possesses a peak at 5.8,u and in thatthe peak at 2.9a (H O) is absent. Also, the monohydrate lacks a peak at6.0,u. The monohydrate upon treatment with Water reverts back to thedihydrate.

Example 14.Preparation of 1-(butylcarbamoyl)-2 benzimidazolecarbarnicacid, methyl ester 2:1 zinc complex (anhydrous form) C23H34N8O6ZD.

(percent): C, 52.3; H, 5.3; N, 17.4. Found (percent):

C, 52.25; H, 5.10; N, 17.34.

The infrared spectrum of the anhydrous product differs from that of thedihydrate mainly in that the peak at 2.9;1. is attributable to water hasdisappeared, and in that a new peak is present at 58a. The anhydrousmaterial upon treatment with water reverts back to the dihydrate.

Example 15.Preparation of l-(butylcarbamoyD-Z- 'benzimidazolecarbamicacid, methyl ester 2:1 manganese complex, monohydrate Ten parts of thedihydrate of Example 2 are placed in a rotary laboratory evaporatorunder a high vacuum (0.25 mm./Hg). The temperature is graduallyincreased to 60 C. and kept at that level for 3 hours. The monohydrateobtained weighs 9 parts and analyzes as follows:

Calc. for the 2:1 manganese complex, monohydrate C2 H3 N OqMI1(percent): C, H, N, 17.2. Found (percent): C, 51.83; H, 5.73; N, 17.12.

The infrared spectrum of the monohydrate product differs from that ofthe dihydrate mainly in that it contains a new peak at 5.8; and that thepeak at 2.9 attributable to water has disappeared completely, eventhough the molecule still contains one mole of water. Upon treatmentwith water, the monohydrate reverts back to the dihydrate.

Example 16.Preparation of 1 (butylcarbamoyl) 2- benzimidazolecarbamicacid, methyl ester 2:1 manganese complex (anhydrous form) Ten parts ofthe dihydrate of Example 2 and parts of Linde Molecular Sieve Type 3Aare added to 50 parts by volume of dimethylformamide. The mixture isstirred for 1 /2 hours and filtered. The filtrate is placed in a rotarylaboratory evaporator and concentrated in a high vacuum (0.25 mm./Hg) at50 C. After removal of most of the dimethylformamide, the temperature isincreased to 70 C., and drying is continued until the residue is a drypowder. The product, which weighs 9 parts, analyzes as follows:

Calc. for the anhydrous 2:1 manganese complex C H N O Mn (percent): C,53.1; H, 5.4; N, 17.7. Found(percent): C, 52.90; H, 5.72; N, 17.81.

If this drying experiment is repeated in the absence of Linde MolecularSieve, the same product is obtained. In other words, treatment of thedihydrate with dimethylformamide and removal of this solvent byevaporation in vacuum at elevated temperature is suificient to removethe two moles of water of hydration. However, the presence of dryingagent is advantageous in that it produces a dry dimethylformamidedistillate which can be used as such for drying the next batch ofmaterial. The infrared spectrum of this anhydrous material resemblesthat of the monohydrate of Example 15 in that both spectra (unlike thatof the dihydrate of Example 2) have a peak at 5.8a and no peak at 2.9a(H O). The spectrum of the anhydrous product has an extra peak at 5.952. Upon treatment with water, the anhydrous material is converted backto the dihydrate.

Example 17 The following zinc complexes can be prepared similarly bysubstituting the corresponding 2-benzimidazolecarbamio acid, alkyl esterreactants for 1-(butylcarbamoyl) 2-benzimidazolecarbamic acid, methylester of Example 1.

1-dodecylcarbamoyl-2-benzimidazolecarbamic acid, methyl ester 2:1 zinccomplex, dihydrate 1- (A-dodecenylcarbamoyl -2-'benzimidazolecarbamicacid, methyl ester 2: 1 zinc complex, dihydratel-(propynylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydratel-(dodecynylcarbamoyl)-2-benzimidazolecarbamic acid,

ethyl ester 2:1 zinc complex, dihydrate 1-(cyclopropylcarbamoyl)-2-benzimidazolecarbamic acid,

sec-butyl ester 2:1 zinc complex, dihydrate1-(cyclooctylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydrate 1-(p-methylcyclohexylcarbamoyl)-2-benzimidazolecarbamic acid, isopropyl ester 2:1 zinc complex,dihydrate 1- (cyclohexylmethylcarbamoyl) -2-b enzimidazolecarbamic acid,methyl ester 2:1 Zinc complex, dihydrate 1-(m-methoxycyclohexylcarbamoyl) -2-benzimidazolecarbamic acid, methylester 2:1 zinc complex, dihydrate 1-(p-chlorocyclohexylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester2:1 zinc complex, dihydrate1-(2-cyclopentenylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester2:1 zinc complex, dihydrate 1- 2-cyclohexenylcarbamoyl-2-benzimidazolecarbamic acid, methyl ester 2: 1 zinc complex, dihydrate1- (2-cyclooctenylcarbamoyl -2-benzimidazolecarbamic acid, sec-butylester 2 :1 zinc, dihydrate1-(2-cyclobutenylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester2:1 zinc complex, dihydrate1-(norbornylmethylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester2: 1 zinc complex, dihydrate1-(cyclohexylethylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester2:1 zinc complex, dihydrate l-(phenylcarbamoyl)-2-benzimidazolecarbamicacid,

methyl ester 2: 1 zinc complex, dihydrate 1-( butylcarbamoyl-4-methyl-2-benzimidazolecarbamic acid, methyl ester 2:1 zinc complex,dihydrate 1- butylcarbamoyl) -5-butyl-2-benzimidazolecarb amic acid,ethyl ester 2:1 zinc complex, dihydrate 1- (m-tolylcarbamoyl-4-br0mo-2-benzimidazolecarbamic acid, methyl ester 2:1 zinc complex,dihydrate 1- (p-tolylcarbamoyl -2-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydrate 1- (p-ethylphenylcarbamoyl)-5-chloro-2-benzimidazolecarbamic acid, methyl ester 2:1 Zinc complex,dihydrate 1- (butylcarbamoyl -5-fluoro-2-benzimidazolecarbamic acid,methyl ester 2:1 zinc complex, dihydrate 1-(butylcarbamoyl)-4-fluoro-2-benzimidazolecarbamic acid, methyl ester 2:1zinc complex, dihydrate 1-(octylcarbamoyl)-4-nitro-2-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydrate 1- ethylcarhamoyl-4-methoxy-2-benzimidazolecarbamic acid, methyl estre 2:1 zinc complex,dihydrate 1- allylcarb amoyl -5-butoxy-2-benzimidazolecarbamic acid,isopropyl ester 2:1 zinc complex, dihydrate1-(p-methoxyphenylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester2:1 zinc complex, dihydrate 1- (p-ethoxyphenylcarb amoyl-2-benzimidazolecarbamic acid, methyl ester 2:1 zinc complex, dihydrate1 1- (p-nitrophenylcarbamoyl -2-benzimidazolecarbamic acid, methylester'2:l zinc complex, dihydrate1-(m-trifluoromethylphenylcarbamoyl)-2-benzimidazolecarbamic acid, ethylester 2:1 zinc complex, dihydrate1-(p-methylsulfonylphenylcarbamoyl)-2-benzimidazolecarbamic acid,isopropyl ester 2: l zinc complex, dihydrate1-(p-chlorophenylcarbamoyl)-2-berizimidazolecarbamic acid, methyl ester2:1 zinc complex, dihydrate1-(3,4-dichlorophenylcarbamoyl)-2-benzirnidazolecarbamic acid, methylester 2:1 zinc complex, dihydratel-(m-bromophenylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester2:1 zinc complex, dihydrate 1- (o-fluorophenylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 2:1 zinc complex, dihydratel-(benzylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydrate 1- benzylcarbamoyl-5-nitro-2-benzimidazolecarbamic acid, isopropyl ester 2:1 zinc complex,dihydrate l-(o-methylbenzylcarbamoyl)-2-benzimidazolecarbamic acid,methyl ester 2:1 zinc complex, dihydrate1-(p-methylbenzylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester2:1 zinc complex, dihydratel-(p-nitrobenzylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 2:1 zinc complex, dihydrate 1- p-methoxybenzylcarbamoyl-2-benzimidazolecarb amic acid, methyl ester 2:1 zinc complex, dihydrate1-(o fluorobenzylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester2:1 zinc complex, dihydrate1-(p-chlorobenzylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester2: l zinc complex, dihydrate1-(m-bromobenzylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 2:l zinc complex, dihydrate l-(carbamoyl)-2-benzimidazolecarbamic acid,methyl ester 2:1 zinc complex, dihydratel-(formyl)-2benzimidazolecarbamic acid, methyl ester 2:1 zinc complex,dihydrate l-(acetyl)-2-benzimidazolecarbamic acid, methyl ester 2:1 Zinccomplex, dihydrate l-(propionyl)-2-benzimidazolecarbamic acid, methylester 2:1 zinc complex, dihydrate l-(dodecanoyl)-2-benzimidazolecarbamicacid, methyl ester 2:1 zinc complex, dihydrate1-(cyanoacetyl)-2-benzimidazolecarbamic acid, sec-butyl ester 2:1 zinccomplex, dihydrate1-(3-methoxypropionyl)-5-nitro-2-benzimidazolecarbamic acid, methylester 2:1 zinc complex, dihydrate1-(3-sec-butoxypropionyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydratel-(acetoacetyl)-2-benzimidazolecarbamic acid, methyl ester 2:1 zinccomplex, dihydrate 1- (levulinyl) -2-benzimidazolecarbamic acid, methylester 2:1 zinc complex, dihydrate1-(4-chlorocaproyl)-2-benzimidazolecarbamic acid, methyl ester 2:1 zinccomplex, dihydrate 1- (trifluoroacetyl) -2-benzimidazolecarbamic acid,

methyl ester 2:1 Zinc complex, dihydratel-(acroyl)-2-'benZimidazolecarbamic acid, ethyl ester 2:1

zinc complex, dihydrate l-(A -decenoyl)-2-benzimidazolecarbamic acid,isopropyl ester 2:1 Zinc complex, dihydrate l-( cyclopropylcarbonyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydrate1-(cyclooctylcarbonyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydrate l-(propargyl)-2benzimidazolecarbamic acid, isopropyl ester 2:1 zinc complex, dihydrate1-(benzoyl)-2-benzimidazolecarbamic acid, methyl ester 2:1 zinc complex,dihydrate l-(p-chlorobenzoyl)-2-benzimidazolecarbamic acid, methyl ester2:1 zinc complex, dihydrate 1- (m-bromobenzoyl)-2-'benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydrate.l-(p-fiuorobenzoyl)-2-benzimidazolecarbamic acid, methyl ester 2:1 zinccomplex, dihydrate 1-( p-methylbenzoyl) -2-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydrate 1- (p-sec-butylbenzoyD-2-benzimidazolecarbarnic acid,

methyl ester 2:1 zinc complex, dihydratel-(m-nitrobenzoyl)-2-benzimidazolecarbamic acid, methyl ester 2:1 Zinccomplex, dihydrate 1- (p-methoxybenzoyl) -2-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydratel-(p-butoxybenzoyl)-2-'benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydrate 1-'( methylthiocarbonyl-2-benzimidazolecarbamic acid,

methyl ester 2:1 Zinc complex, dihydrate 1- (dodecylthiocarbonyl-2-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydrate l- 2-cyanoethyloxythiocarbonyl-Z-b enzimidazolecarbamic acid, methyl ester 2:1 zinccomplex, dihydrate 1- 2-hydroxyethyloxy)thiocarbonyl-2-benzimidazolecarbamic acid, methyl ester 2:1 Zinccomplex, dihydrate 1- 3-methoxypropyloxy)thiocarbonyl-Z-benzimidazolecarbamic acid, methyl ester 2:1 zinccomplex, dihydrate 1- (3 -sec-'butoxypropyloxy)thiocarbonyl-Z-benzimidazolecarbamic acid, ethyl ester 2:1 Zinc complex,dihydrate l-(Z-chloroethyloxy)thiocarbonyl-Z-benzimidazolecarbamic acid,methyl ester 2 :1 zinc complex, dihydrate 1- 3-bromopropyloxythiocarbonyl-2-benzimidazolecarbamic acid, methyl ester 2:1 zinccomplex, dihydrate 1- allylthio carbonyl-Z-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydrate 1-(2-butenylthio)carbonyl-Z-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydrate 1- a-decenyloxythiocarbonyl-Z-benzimid azolecarbamic acid, methyl ester 2:1 zinccomplex, dihydrate 1- (cyclopropylthio) carbonyl-2-benzimidazolecarbamicacid, methyl ester 2:1 Zinc complex, dihydrateZ-(methoxycarbonylamino)-1-dithiobenzimidazolecarboxylic acid, methylester 2:1 zinc complex, dihydrate 2- (methoxycarbonylamino)l-thiono'benZimidazolecarboxylic acid, (3-decyn-1-yl) ester 2:1 zinccomplex, dihydrate 2- (methoxycarbonylamino) -l-thionobenzimidazolecarboxylic acid, cyclooctyl ester 2:1 zinc complex,dihydrate 2-(methoxycarbonylamino) -1-thionobenzimidazolecar- 'boxylicacid, cyclohexyl methyl ester 2:1 zinc complex, dihydrate 2-(methoxycarbonylamino) l -dithiobenzimidazolecarboxylic acid, norbornylmethyl ester 2:1 zinc complex, dihydrate 2 methoxycarbonylamino-l-thionobenzimidazolecarboxylic acid, cyclooctyl methyl ester 2:1 zinccomplex, dihydrate2-(ethoxycarbonylamino)-1-thionobenzimidazolecarboxylic acid, propargylester 2:1 zinc complex, dihydrate 1- (phenylthio)carbonyl-Z-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydrate 2- (methoxycarbonylaminol-thionobenzimidazolecarboxylic acid, phenyl ester 2:1 zinc complex,dihydrate 1- benzylthio) carbonyl-2-benzimidazolecarbamic acid,

isopropyl ester 2:1 zinc complex, dihydrate 2- (methoxycarbonylamino-1-thionobenzimidazolecarboxylic acid, benzyl ester 2:1 zinc complex,dihydrate 2-(methoxycarbonylamino) -1-dithiobenzimidazolecarboxylicacid, benzyl ester 2:1 zinc complex, dihydrate 2- (methoxycarbonylamino)-1-dithiobenzimidazolecarboxylic acid, p-chloroberizyl ester 2:1 zinccomplex, dihydrate 2- methoxycarbonylamino)-1-dithiobenzimidazolecarboxylic acid, p-bromophenyl ester 2:1 zinccomplex, dihydrate 2- methoxycarbonylamino)l-thiolbenzimidazolecarboxylic acid, p-methylbenzyl ester 2:1 zinccomplex, dihydrate 2- (methoxycarbonylamino)-l-thiolbenzimidazolecarboxylic acid, p-butylphenyl ester 2:1 zinccomplex, dihydrate2-(methoxycarbonylamino)-1-thi0lbenzimidazolecarboxylic acid,p-nitrophenyl ester 2:1 zinc complex, dihydrate 2- methoxycarbonylamino)l -thiolbenzimidazolecarboxylic acid, p-nitrobenzyl ester 2:1 zinccomplex, dihydrate 2- (methoxycarbonylaminol-thionobenzimidazolecarboxylic acid, p-methoxyphenyl ester 2:1 zinccomplex, dihydrate 2- (methoxycarbonylamino-1-thionobenzimidazolecarboxylic acid, p-butoxybenzyl ester 2:1 zinccomplex, dihydrate2-(methoxycarbonylamino)-1-dithiobenzimidazolecarboxylic acid, phenylester 2:1 zinc complex, dihydrate l-(methylthio)-2-benzimidazolecarbamic acid, methyl ester 2:1 zinc complex, dihydrate1-(isopropylthio)-2-benzimidazolecarbamic acid, methyl ester 2:1 zinccomplex, dihydrate l-(propylthio)-2 benzimidazolecarbamic acid, methylester 2:1 zinc complex, dihydrate l- (trichloromethylthio)-2-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydrate 1- (trichloromethylthio)-2-benzimidazolecarbamic acid,

ethyl ester 2:1 zinc complex, dihydrate1-(trichloromethylthio)-2-benzimidazolecarbamic acid,

isopropyl ester 2:1 zinc complex, dihydrate l-(3-chloropropylthio)-2-benzimidazolecarbamic acid,

methyl ester 2: l zinc complex, dihydrate 1- pentachloroethylthio)-2-benzimidazolecarbamic acid,

methyl ester 2: 1 zinc complex, dihydrate l- (phenylthio)-2-benzimidazolecarbamic acid,

methyl ester 2: l zinc complex, dihydratel-(benzylthio)-2-benzimidazolecarbamic acid,

methyl ester 2: l zinc complex, dihydrate1-(o-nitrophenylthio)-2-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydrate 1- 2,4-dinitrophenythio-2-benzimidazolecarbamic acid,

methyl ester 2: l zinc complex, dihydrate 1- (p-chlorophenylthio-2-benzimidazolecarb amic acid,

methyl ester 2:1 zinc complex, dihydratel-(m-tolylthio)-2-benzimidazolecarbamic acid,

methyl ester 2:1 zinc complex, dihydrate 1- (o-nitrobenzylthio)-2-benzimidazolecarbamic acid,

methyl ester 2: l zinc complex, dihydrate1-(p-chlorobenzylthio)-2-benzimidazolecarbamic acid,

methyl ester 2: 1 zinc complex, dihydrate lp-methylbenzylthio-2-benzimidazolecarbamic acid,

sec-butyl ester 2: l zinc complex, dihydrate 1-( o-nitrobenzylthio)-2-benzimidazolecarbamic acid,

isopropyl ester 2: 1 zinc complex, dihydrate Example 18 The zinccomplexes of Example 17 are dried as described in Example 14. Thecorresponding anhydrous forms of the products of Example 17 areobtained.

Example 19 The following manganese complexes can be prepared bysubstituting equivalent amounts of the correspondingZ-benzimidazolecarbamic acid, alkyl esters forl-(butylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester in Example2.

l-(benzylcarbamoyl)-2-'benzimidazolecarbamic acid,

methyl ester 2:1 manganese complex, dihydratel-(methylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2: l manganese complex, dihydrate 1-( octylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 2: l manganese complex,dihydrate lallylcarbamoyl -2-benzimidazolecarbamic acid, methyl ester 2:1 manganese complex, dihydrate l-(hexylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 2: 1 manganese complex,dihydrate 1- (p-nitrophenylcarbamoyl) -2-benzimidazolecarbamic acid,methyl ester 2: 1 manganese complex, dihydratel-(butylcarbamoyh-2-benzimidazolecarbamic acid,

isopropyl ester 2: l manganese complex, dihydrate 1-(p-methoxyphenylcarbamoyl) -2-benzimidazolecarbamic acid, methyl ester2: 1 manganese complex, dihydrate 1-( norbornylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2: 1 manganese complex, dihydrate1(cyc1ohexylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2: 1 manganese complex, dihydrate1-(phenylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 manganese complex, dihydrate 1- cyclopropylcarbonyl-2-b enzimidazolecarbamic acid,

methyl ester 2:1 manganese complex, dihydrate l-(propionyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 manganese complex, dihydrate l- (benzoyl-2-benzimidazolecarbamic acid,

methyl ester 2:1 manganese complex, dihydrate ltrichloromethylthio)-2-benzimidazolecarbamic acid,

methyl ester 2: 1 manganese complex, dihydrate l-(trichloromethylthio-2-benzimidazolecarbamic acid,

isopropyl ester 2:1 manganese complex, dihydrate 1-(cyclohexylmethylcarbamoyl -2-benzimidazolecarbamic acid, methyl ester2: 1 manganese complex, dihydrate l- 2,4-dinitrophenylthio-2-benzimidazolecarbamic acid,

methyl ester 2: l manganese complex, dihydrate1-(2,4-dinitrophenylthio)-2-benzimidazolecarbamic acid,

isopropyl ester 2:1 manganese complex, dihydrate Example 20 Thedihydrates of Example 19 are dried by the method of Example 16. Thecorresponding anhydrous forms are obtained.

Example 21 The following copper complexes can be prepared bysubstituting equivalent amounts of the corresponding 2-benzimidazolecarbamic acid, alkyl esters forl-(butylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester in Example3.

l-(benzylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2: 1 copper complex 1-( methylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 copper complexl-(octylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2: 1 copper complex1-(allylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2: 1 copper complex l-(hexylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2: 1 copper complex 1- (p-nitrophenylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 2: 1 copper complexl-(p-methoxyphenylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester2: 1 copper complex 1-(cyclohexylcarbamoyl)-2-benzimidazolecarbamicacid,

methyl ester 2: 1 copper complexl-(phenylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 copper complex1-(cyclohexylmethylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester2: 1 copper complex l-(cyclopropylcarbonyl) -2-benzimidazolecarbamicacid,

methyl ester 2:1 copper complex 1- (propionyl -2-benzimidazolecarbamicacid,

methyl ester 2: 1 copper complex 1- benzoyl -2-benzimidazolecarbamicacid,

methyl ester 2: 1 copper complex 1- (trichloromethylthio-2-benzimidazolecarbamic acid,

methyl ester 2:1 copper complexl-(2,4-dinitrophenylthio)-2-benzimidazolecarbamic acid,

methyl ester 2:1 copper complex l-(acetyl)-2-benzimidazolecarbamic acid,methyl ester 2: 1 copper complex Example 22 The following nickelcomplexes can be prepared by substituting equivalent amounts of thecorresponding 2- benzimidazolecarbamic acid, alkyl esters for l-(butyl-19 carbamoyl)-2-benzimidazolecarbamic acid, methyl ester in Example 4.

l-(allylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 2:1 nickelcomplex, trihydrate 1-(hexylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2: l nickel complex, trihydratel-(propionyl)-2-benzimidazolecarbamic acid, methyl ester 2:1 nickelcomplex, trihydrate 1- p-methoxyphenylcarbamoyl) 2-benzimidazolecarbamicacid, methyl ester 2:1 nickel complex, trihydratel-(benzoyl)2-benzimidazolecarbamic acid, methyl ester 2:1 nickelcomplex, trihydrate l-(trimethylthio)-2-benzimidazolecarbamic acid,methyl ester 2:1 nickel complex, trihydrate1-(2,4-dinitrophenylthio)-2-benzimidazolecarbamic acid,

methyl ester 2:1 nickel complex, trihydrate Example 23 The followingcobalt complexes can be prepared by substituting equivalent amounts ofthe corresponding 2- benzimidazolecarbamic acid, alkyl esters forl-(butylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester in Example5.

1- (hexylcarbamoyl -2-benzimidazolecarb amic acid,

methyl ester 2:1 cobalt complex, dihydratel-(octylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 cobalt complex, dihydrate1-(p-methoxyphenylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester2: 1 cobalt complex, dihydratel-(benzylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 cobalt complex, dihydratel-(cyclohexylcarbamoyl)-27benzimidazolecarbamic acid,

methyl ester 2:1 cobalt complex, dihydrate1-(acetyl)-2-benzimidazolecarbamic acid, methyl ester 2:1 cobaltcomplex, dihydrate 1-(trichloromethylthio)-2-benzimidazolecarbamic acid,

methyl ester 2:1 cobalt complex, dihydrate1-(p-nitrophenylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 2:l cobalt complex, dihydrate 1-( cyclopropylcarbonyl)-2-benzimidazolecarbamic acid,

methyl ester 2 :1 cobalt complex, dihydratel-(benzoyl)-2-benzirnidazolecarbamic acid, methyl ester 2:1 cobaltcomplex, dihydrate 1- 2,4-dinitrophenylthio -2-benzimidazolecarbamicacid,

methyl ester 2:1 cobalt, dihydrate Example 24 The following transitionmetal complexes can be prepared by substituting equivalent amounts ofthe appropriate soluble salts for the zinc acetate dihydrate in Example1.

l-(butylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester 2:1 iron complex, dihydrateI-(butylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester 2:1cadmium complex, dihydrate 1- butylcarbamoyl -2-benzimidazolecarbamicacid, methyl ester 2:1 chromium complex, dihydrate As mentionedpreviously, it has been found that the complexes of this inventionpossess outstanding fungicidal and mite ovicidal activity when employedto prevent or mitigate damage to plants and inanimate organic materials.The paragraphs which follow describe in more detail the utility of thisinvention.

The complexes of the invention control a wide variety of fungus diseasesof foliage, fruit, stems and roots of growing plants without damage tothe host. Fruits, tubers, bulbs, roots, seeds and other plant partsharvested for food, animal feed or for other purposes are protected fromfungus deterioration during processing, distribution and storage. Seeds,tubers, cuttings and other plant propagation materials are protectedfrom fungus attack during handling and storage, as well as in the soilafter planting. Wood, fabric, fiber board, paper and other industrialmaterials are protected from unsightly stain and destructive decaycaused by fungi. Luggage, shoes, shower curtains, carpets, mats,clothing and other useful household, public or industrial items areprotected from rot, fungus stains and mold growth. Painted surfaces areprotected from stain and discoloration by incorporation of a complex ofthis invention in the paint formulation.

The many fungi against which the complexes of this invention are activemay be represented by, but is not intended to be limited to, thefollowing: Venturia inaequalis, which causes apple scab; Podosphaeraleucotriclza, which causes powdery mildew on apples; Ul'omycesplzaseoli, which causes bean rust; Cercospora apii, which causes earlyblight of celery; Cercospora beticola, which causes leaf spot of sugarbeets; Sclerotinia scleroliorum, which causes rot of vegetable crops,such as lettuce, beans, carrots, and celery; Colletotrichum spp., whichcauses anthracnose of fruits and vegetables, such as beans, tomatoes andcoffee; Septoria apii, which causes late blight of celery; Cercosporamusae, which causes Sigotoka disease of banana; Piricularia spp., whichcauses Johnson spot on banana; Erysiphe cichoracearum, which causespowdery mildew on cantaloupe and other cucurbit crops; Penicilliumdigitatum, Phornopsis supp., and Diplodia natalensz's, which cause fruitrots on citrus; Ceratostomella ulmi, which causes Dutch elm disease;Sphaerotheca humuli, which causes powdery mildew on roses; Diplo-'carpon roeae, which causes black spot on roses; Ramularia spp., whichcauses leaf spots on ornamental plants; Botrythis cinerea, which causesblossom and fruit rots of omamentals, fruits and vetgetables; Uncinulanecator, which causes powdery mildew on grapes; Guignal'dia bidwellii,which causes grape black rot; Melonconium fuligineum, which causes whiterot of grapes; Coccomyces hiemalz's, which causes cherry leaf spot;Cytospora spp., which cause cankers of trees; Cladosp oriumcal-pophilum, which causes peach scab; Fusicladiumi efiusum, whichcauses pecan scab; Erysiphe graminis, which causes powdery mildew oncereals; Monolinia (Sclerotinia) laxa. and M. fructicola, which causebrown rot of stone fruits, such as peaches, cherries and apricots;Pseudopenziza ribes, which causes leaf spot on gooseberry; Piriculariaoryzae, which causes rice blast; Puccinia recondita, P. coronata and P.glumarum, which cause leaf rusts of wheat, oats and grasses,respectively; Puccim'a graminis tritici, which causes stem rust ofwheat; Claviceps purpurea, which causes ergot of rye and grasses;Aspergillus niger, which causes cotton boll rot as well as decay following wounding in many plant tissues; Aspergillus terreus, which iscommon in soil and attacks vegetable matter; Tilletia caries and othertilletia species, which cause common bunt of wheat; Ustilago tritici,Uszilago nigra, Ustilago avena (and other Ustilago species), which causeloose smut of wheat, barley, and oats, respectively; Urocystz's triticiand other Urocystis species, which cause loose smut of wheat;Sphacelotheca sorghi, which causes covered smut of soghum; Ustilagohordei and Ustilago kolleri, which cause covered smut of barley andoats, respectively; Pithomyces char-forum; which is present in turf,pastures, and other grassy areas and is known to have several secondaryeffects; various species of Rhizoctonia, Fusarium and Verticilliumpresent in soil and attacking the roots or other underground parts andthe vascular system of a variety of plants; various species ofPenicillium growing on such things as fabric, fiber board, leather goodsand paint; species of Myrothecium attacking such items as showercurtains, carpets, mats and clothing.

The mite ovicidal action of the complexes of this invention is useful inpreventing the development of damaging populations of mites or incausing the gradual reduction of existing populations. The movement ofmites is limited. Thus, an increase in population or the continuation ofa high population in a particular locus depends largely upon thehatching of eggs laid in that locus.

Mite eggs do not hatch to produce living young if these eggs are treatedwith one of these complexes, or if they are laid on a surface containingone of these complexes. Further, the eggs will not hatch if they arelaid by a female mite that has been in contact with one of thesecomplexes, or are laid by a female mite that is ingesting or hasrecently ingested food such as plant juices containing one of thesecomplexes. This interference with the hatching of eggs prevents thepopulation from increasing significantly beyond that present at the timeof treatment. Also, this ovicidal action, along with the high naturalmortality of adults, can largely eliminate mites from an alreadyinfested area over a relatively short period of time. Further as long asthe complexes are present on the surface the mites occupy or remain intheir food supply, new populations cannot develop.

Many species of mites which cause damage to fruits, field crops,vegetables, and ornamentals under a wide variety of circumstances, arecontrolled by the complexes and methods of this invention. The extent ofthe practical utility of the mite control obtained is represented by,but is not intended to be limited to, the following listing of specificsusceptible mites along with the types of damage that they can cause:

Panonychus ulmi (European red mite) and Tetranychus urticae (two-spottedmite) which are commonly called orchard mites, these mites attack agreat many deciduous tree fruits including apples, pears, cherries,plums and peaches; T etranyclzus atlanticus (Atlantic or strawberryspider mites), T. cinnabarinus (carmine spider mite) and T. pncificus(Pacific spider mite), these mites attack cotton and numerous other cropplants; Paratetranychus citri (citrus red mite) and others which attackcitrus; Phyllocoptruta sleivora, which causes citrus rust; Bryobiapraetiosu (clover mite) which attacks clover, alfalfa and other crops;Acerz'a neocynodomis which attacks grasses and other plants; Ty'rophaguslintneri which is a serious pest in stored foods and on cultivatedmushrooms and Lepidoglyphus destruclor which injures Kentucky bluegrassseed in storage.

The complexes of this invention when applied by certain of the methodsof this invention enter and move freely within plants, i.e., they aresystemic. Thus, both fungi and mites can be controlled in plants inparts well removed from the point of application. In view of thisactivity the complexes can be applied to seeds; thus the treatment ofcucumber seeds with a few grams per 50 kilograms of seed of a complex ofthis invention provides control of powderly mildew (Erysiphecichoracearum) and spider mites such as Tetranychus urticae on theresulting plants for periods in excess of 40 days. Applications to soilalso provides control of certain foliage diseases and mites on plantsgrowing in the treated soil. Spray or dust treatments of plant foliageand stems impart protection against both fungi and mites to other partsof the plant not actually sprayed and to new foliage developing later.

An additional valuable characteristic of the complexes of this inventionis their ability to prevent the spread or to kill fungus infectionalready established within a plant, i.e. they are curative. Thus, thecomplexes need not be applied until after conditions develop whichpermit the actual initiation of fungus attack. This means that, undersome circumstances, it is possible to avoid applying any chemical duringthe entire life of the crop, In other cases, only a part of the normalfull schedule of pesticide application is required.

Therefore great savings both in chemical cost and ap plication labor arepossible with compounds capable of systemic and curative performance,Another saving is afforded by the complexes of this invention throughthe fact that both fungi and mites are controlled by applications of asingle chemical.

The complexes of this invention provide protection from damage caused byfungi, mites or both when applied to the proper locus by the methodsdescribed hereinafter and at a suflicient rate to exert the desiredfungicidal and mite ovicidal effect. They are especially suited for theprotection of living plants such as fruit-bearing trees, nut-bearingtrees, ornamental trees, forest trees, vegetable crops, horticulturalcrops (including ornamentals, small fruits and berries), fiber crops,grain and seed crops, sugarcane, sugar beets, pineapple, forage and haycrops, beans, peas, soybeans, peanuts, potatoes, sweetpotatoes, tobacco,hops, turf and pasture.

Living plants may be protected from fungi and mites by applying one ormore of the complexes of this invention to the soil in which they aregrowing or in which they may subsequently be seeded or planted; or toseeds, tubers, bulbs or other plant reproductive parts prior toplanting; as well as to foliage, stems and fruit of the living plant.Living plants can also be protected by dipping the root system orphysically injecting the chemical or chemicals into roots or stems.

Soil applications are made from dusts, granules, pellets, slurries orsolutions. Preferred rates for application of the complexes of thisinvention to soil in which plants are or will be growin range from 0.01to 500 parts per million by weight of the soil in which the roots are orwill be growing. More preferred use rates are in the range of 0.1 to 50parts per million, and the most preferred rates are in the range of 0.25to 25 parts per million.

Preferred rates for application to seeds, tubers, bulbs or other plantreproductive parts, range from 0.03 to 6000 grams of active complex ofthis invention per 50 kilograms of planting material treated. Morepreferred rates are in the range of 0.3 to 3000 grams of active complexper 50 kilograms. The most preferred rates are in the range of 2.8 to1500 grams per 50 kilograms.

Applications are made from dusts, slurries or solutions. Such treatmentsprotect the treated parts themselves from damage due to fungi, mites, orboth, and in addition, impart extended protection against both types ofpests to the resulting new plants.

Preferred rates for application of the complexes of this invention tofoliage, stems and fruit of'living plants range from 0.012 to 60kilograms of active ingredient per hectare. More preferred rates are inthe range of 0.025 to 30 kilograms per hectare and the most preferredrates are in the range of 0.05 to 15 kilograms per hectare The optimumamount within this range depends upon a number of variables which arewell-known to those skilled in the art of plant protection. Thesevariables include, but are not limited to, the disease to be controlled,weather conditions expected, the type of crop stage of development ofthe crop, and the interval between applications. Applications within therange given may need to be repeated one or many more times at intervalsof 1 to 60 days. Applications are made from dusts, slurries orsolutions.

Preferred rates for dip applications to roots of living plants are inthe range of 0.5 to 18,000 grams of active ingredient per 380 liters ofwater or other liquid carrier. More preferred rates are in the range of4.5 to 9,000 grams per 380 liters and the most preferred rates are inthe range of 45 to 4500 grams per 380 liters.

Preferred rates for injection into the roots or stems of living plantsare in the range of 0.01 to 10,000 parts per million of water or otherliquid carrier. More preferred rates are in the range of 0.1 to 5,000parts per million. The most preferred rates are in the range of 1 to1,000 parts per million.

Plant parts such as fruits, tubers, bulbs, foliage, roots and the like,harvested for food or feed, are protected from decay and otherdeterioration caused by fungi or mites during processing, distributionand storage by treatment with an active complex of this invention. Theplant parts to be so protected can be dipped in a liquid bath containingthe active ingredient, dusted with a finely divided preparation of theactive ingredient, sprayed, misted with an aerosol containing thecompound, or enclosed in wrapping or packing materials impregnated withthe active compound.

If a liquid bath is used, it can contain an amount of the activeingredient in the range of 1 to 5,000 parts per million of the weight ofthe fluid. A more preferred range for the bath is 5 to 2,500 parts permillion, and the most preferred range is to 1,000 parts per million.

Dusts as well as wrapping or packing materials used for this type ofapplication can contain 0.01 to 10% of the active ingredient. Morepreferred rates are in the range of 0.1 to 5% and the most preferredrates are in the range of 0.2 to 2.5%.

Wood, leather, fabric, fiber board, paper and other industrial materialsof an organic nature can be protected from decomposition ordiscoloration by fungi and infestation by mites by coating,incorporating or impregnating with an effective amount of one or more ofthe complexes of this invention. The coating can be accomplished bydipping, spraying, flooding, misting (as with an aerosol) or dusting thematerial to be protected with a suitable composition containing theactive ingredient. The preferred use rates for the active ingredient inthe treating preparation actually applied to the material to beprotected are in the range of 0.025 to 95% by weight. More preferredrates are in the range of 0.05 to 50%, With the most preferred ratesbeing in the range of 0.1 to

Where incorporation or impregnation procedures are to be employed, userates may be expressed in terms of the amount of active ingredientintroduced into the material to be protected. The preferred use ratesfor these types of applications are in the range of 0.001 to 30 percentby Weight of active ingredient in the final product. More preferredrates are in the range of 0.005 to 15% with the most preferred ratesbeing in the range of 0.01 to 7%.

Luggage, shoes, shower curtains, carpets, mats, clothing and otheruseful household, public or industrial items are protected from rot,fungus stains and unsightly mold growth as well as infestation by mitesby the active complexes of this invention. Again, either surface of deepprotection can be obtained. Surface treatment is by dips, washes,sprays, aerosols or dust applications. Deep treatment is accomplished bypenetrating solutions. Sprays, dips and washes contain the activecompound of the invention at rates of 10 to 5,000 parts per million.Fluids for aerosol application and dusts contain 0.1 to 20% by weight.Penetrating solvent solutions contain an amount of the active ingredientthat results in a deposit of 5 to 20,000 parts per million in thematerial to be protected.

Painted surfaces can be protected from unsightly stain and mold growthby incorporating in the paint formulation, prior to application, 5 to20,000 parts per million of an active complex of this invention. Morepreferred rates are in the range of 10 to 10,000 parts per million andthe most preferred rates are in the range of 20 to 5,000 parts permillion. Such treatments with the complexes of this invention alsoprotect the paint while still in the can from deterioration by fungi.

Damage by mites to stored organic products such as grain, seed, bulbs,tubers, meat or animal hides is kept to a minimum by treating thefloors, walls, portions, and other parts of Warehouses or otherstructures with one or more of the active complexes. Applications aremade by the use of dusts, sprays, or aerosols with preferred use ratesin the range of 0.05 to 1,000 grams of the active complex of thisinvention per 93 square meters of surface to be kept free of excessivemite populations.

Curative control of plant diseases with the complexes of this inventionis enhanced if the treated plant parts are moist for one or more periodsof 2 to 12 hours each soon after the active complex is applied. Oftenthe slow drying of an original spray treatment or naturally occurringrains, mists, fogs or dews will accomplish this. Under othercircumstances, such as during dry periods or in shelters such asgreenhouses, it is necessary to keep the plants moist by some specialeffort for best results.

When the complexes of this invention are applied, their activity may beenhanced by using certain adjuvants, for example in the Water in whichthey are dispersed. These adjuvants may be surface-active agents, oils,humectants, enzymes, carbohydrates, and organic acids. They improve theperformance on tubers, on foliage, in treatments used for dipapplication to rooms of living plants, in the case of liquids used forinjection into the roots or stems of living plants, or in mixtures usedto treat fruits, tubers, bulbs, roots, and the like, after harvest.

Surface-active agents that enhance fungus control and mite control bythe compounds of this invention include sulfonated and sulfated aminesand amides, diphenyl sulfonate derivatives, ethoxylated alcohols,ethoxylated alkylphenols, ethoxylated fatty acids, ethoxylated fattyesters and oils, polyethylene oxide/polypropylene oxide combinations,alkylsulfonates, fluorocarbon surfactants, glycerol esters, ethoxylatedalcohol sulfates, glycol esters, isethionates, sulfated ethoxylatedalkylphenols, lanolin derivatives, lecithin and lecithin derivatives,alkanol amides, phosphate derivatives, monoglycerides and derivatives,quaternaries, sorbitan and sorbitol derivatives, sulfosuccinates,alcohol sulfates, sulfated fatty esters, sulfated and sulfonated oilsand fatty acids, alkylbenzenesulfonates, imidazolines, taurates,ethoxylated mercaptans, ethoxylated amines and amides, modified phthalicglycerol alkyd resins, and similar materials. The oils includenonphytotoxic aliphatic spray oils and triglycerides, either with orwithout emulsifier to permit dispersion in water. Humectants such asglycerin or ethylene glycols, enzymes such as bromelin, andcarbohydrates such as glucose, lactose, and dextrose are also useful.Organic acids of interest include glycolic and gluconic acids. Althoughthe precise manner in which these additives improve the performance ofthe fungicides of this invention is not known, the effect is,nevertheless, startling, and it is possible that these additives improvethe penetration into the plant or translocation throughout the plant ofthe fungicides of this invention.

Preferred surface-active agents to improve the fungicidal and miteovicidal activity of these compounds are products such as dioctyl sodiumsulfosuccinates (Aerosol OT and Aerosol OT-B), blends of aromaticsulfonates and ethylene oxide derivatives (Argrimul GM, Agrimul A-lOO,Agrimul N-lOO, Emcol H50A, Emcol H53), polyoxyethylene sorbitololeate/laurate (Atlox 1045A), sodium lauryl sulfate (Duponol ME),polyoxyethylated vegetable oils (Emulphor EL719), lecithin derivatives(Emultex R), acidic complex organic phosphate esters (Gafac RE610,Victawet), aliphatic amide alkyl sulfonates (Hyfoam Base LL), olei acidesters of sodium isethionate (Igepon AP78), sodium N-methyl-N-oleoyltaurate (Igepon T77), sodium salt of sulfated lauryl and myristylcolamide (Intramin Y), polyethylene glycol 400 oleic acid ester (Nonisol210), sodium dodecylbenzene sulfonate (Sul-Fon-Ate AA 10, Ultrawet K),polyoxyethylene ethers with long-chain alcohols (Surfonic LR 30, Alfonic1012-6, Brij 30, Tergitol TMN), ethylene oxide condensates withpropylene oxide/ethylene diamine condensates (Tetronic 504), polyhydricalcohol esters (Trem 014), modified phthalic glycerol alkyd resins(Triton B 1956), quaternaries (Zelec DP), alkylphenol ethylene oxidecondensates (Dowfax 9N4, Dowfax 9N10, Hyonic 9510, Tergitols) and thelike. Examples given in parentheses are illustrative and do not excludeother unnamed commercial products. Examles of other surface activeagents in each of these several categories are listed in Detergents andEmulsifiers, 1965 Annual, or 1966 Annual, published by John W.

McCutcheon, Inc., 236 Mt. Kemble Avenue, Morristown, NJ.

Preferred oils include spray oils such as Orchex 796 made emulsifiablewtih Triton X45, castor oil made emulsifiable with Triton X-1l4, cornoil made emulsifiable with Triton X-ll4, Volick Oil #70, Sunoco Oil No.7E and similar nonphytotoxic spray oils of vegetable, animal or mineralorigin.

The complexes of this invention and the oils, surfactants, humectants,enzymes, carbohydrates, and acids useful to enhance the fungicidal andmite-ovicidal activity of these complexes can be brought together inseveral ways. For example, the additive which will enhance activity canbe mixed with complexes of the invention when spray slurries are beingprepared. It is often also possible and convenient to produceformulations in which the additive and the complex of the invention willboth be present in the composition, which is then convenient to apply.Such compositions can be powders, granules, suspensions, or evensolutions, depending upon the physical and chemical characteristics ofthe components that are to be prepared. It will be readily understood bythose skilled in the trade and in the light of the above teachings thatthe ratios of active ingredient complex to additives may vary widely.Thus, the additive may be present in such mixtures within the range offrom 33 to 10,000 parts per 100 parts of the complexes of thisinvention. More preferred are rates of from to 5,000 parts of additiveper 100 parts of active ingredient and a range of ratios from to 3,500per 100 parts of complex is even more preferred.

Compositions of this invention are formulated by mixing a complex ofthis invention with one or more surfaceactive agents.

The surface-active agents used in this invention can be wetting,dispersing or emulsifying agents. They may act as wetting agents forWettable powders and dusts, as dispersing agents for Wettable powdersand suspensions and as emulsifying agents for emulsifiable concentrates.Surfactants may also enhance the biological activity of the complexes ofthis invention. Such surface-active agents can include such anionic,cationic and nonionic agents as have heretofore been generally employedin plant control compositions of similar type. Suitable surface-activeagents are set out, for example, in Detergents and EmulsifiersAnnual-4967 by John W. McCutcheon, Inc. Other surface active agents notlisted by McCutcheon but still effective dispersants by virtue ofprotective colloid action include methyl cellulose, polyvinyl alcohol,hydroxyethylcellulose, and alkyl substituted polyvinyl pyrrolidones.

Suitable surface-active agents for use in compositions of this inventioninclude polyethylene glycol esters with fatty and rosin acids,polyethylene glycol ethers with alkyl phenols or with long-chainaliphatic alcohols, polyethylene glycol ethers with sorbitan fatty acidesters and polyoxyethylene thioethers. Other suitable surfactantsinclude amine, alkali and alkaline earth salts of alkyl aryl sulfonicacids, amine, alkali and alkaline earth fatty alcohol sulfates, dialkylesters of alkali metal sulfosuccinates, fatty acid esters of amine,alkali and alkaline earth isethionates and taurates, amine, alkali andalkaline earth salts of lignin sulfonic acids, methylated orhydroxyethylated cellulose, polyvinyl alcohols, alkyl-substitutedpolyvinyl pyrrolidone, amine, alkali and alkaline earth salts ofpolymerized alkylnaphthalenesulfonic acids, and long-chain quatenaryammonium complexes. Anionic and non-ionic surface-active agents arepreferred.

Among preferred wetting agents are sodium alkylnaphthalenesulfonates,sodium dioctylsulfosuccinate, sodium dodecyl benzenesulfonate, ethyleneoxide condensates with alkylated phenols such as octyl-, nonylanddodecyl phenol, sodium lauryl sulfate, and trimethylnonyl polyethyleneglycols. Among preferred dispersing agents are sodium, calcium andmagnesium lignin sulfonates, lowviscosity methyl cellulose,low-viscosity polyvinyl alcohol, alkylated polyvinyl pyrrolidone,polymerized alkylnaphthalenesulfonates, sodium N-oleyl or N-laurylisethionates, sodium N-methyl-N-palmitoyl taurate and dodecylphenolpolyethylene glycol esters.

Among preferred emulsifying agents are ethylene oxide adducts of lauric,oleic, palmitic or stearic acid esters of sorbitan or sorbitol,polyethylene glycol esters with lauric, oleic, palmitic, stearic orrosin acids, oil-soluble alkylarylsulfonates, oil-solublepolyoxyethylene ethers with octyl-, nonyland dodecylphenol,polyoxyethylene adducts to long-chain mercaptans, and mixtures of thesesurfactants.

Compositions of this invention will contain, in addition tosurface-active agents, solid or liquid diluents to produce Wettablepowders, dusts, granules or emulsifiable liquids as desired.

(A) Wettable powders.Wettable powders are compositions which usuallycontain inert solid diluents in addition to surfactants. These inertdiluents may serve several purposes. They can act as grinding aids toprevent mill smear and screen blinding, they can aid rapid dispersion ofthe mix when placed in water, they can adsorb liquid or low-meltingsolid active material to produce a free-flowing solid product, they canprevent agglomeration into lumps upon prolonged hot storage and they canpermit preparation of compositions with a controlled amount of activeingredient so that proper dosage is easily measured by the consumer.

Suitable diluents may be either inorganic or organic in origin. Theseinclude the natural clays, diatomaceous earths, synthetic mineralfillers derived from silica or silicates, blancfixe or barytes,insoluble salts produced by precipitation in fiufiy form such astricalcium phosphate or calcium carbonate, and powdered organic diluentssuch as shell flours, wood flours, corn cob flour, or carbohydrates.Preferred fillers for the compositions of this invention include kaolinclays, attapulgite clay, nonswelling calcium magnesium montmorillonites,synthetic silicas, synthetic calcium and magnesium silicates,diatomaceous silica, sucrose, cob flour and barium sulfate.

Wettable powders will normally contain both a Wetter and a dispersant.Most preferred for dry Wettable powders are those anionic and nonionicsurfactants which exist in solid form. Occasionally a liquid, nonionicsurfactant, normally considered as emulsifying agent can be used toproduce both wetting and dispersion.

Wetting and dispersing agents in Wettable powders of this invention,when taken together, will comprise from about 1.0 weight percent to 8.0weight percent of the total composition. The active component will bepresent at a concentration of from about 25% to and diluent makes up thebalance to Where needed, a corrosion inhibitor or foaming inhibitor maybe added at rates of 0.1% to 1.0% with a corresponding reduction indiluent.

(B) Dusts.Dust compositions are those intended for application in dryform with suitable dusting equipment. Since wind drift is undesirablewhen applying dusts, the most suitable dust diluents are those which aredense and rapid settling. These include kaolinites, talcs,pyrophyllites, ground phosphate rock, Sericite, and ground tobaccostems. However, dusts are usually most easily prepared by diluting anexisting high-strength Wettable powder with a dense diluent so that thefinal dust will frequently contain a fraction of light, absorptivediluent as well as the more desirable dense filler.

A wetting agent is desirable in dust formulations so that adhesion todew-covered foliage is enhanced. Dusts made from Wettable powders willusually contain sufficient wetter, but dusts made directly fromunformulated active will usually contain an added wetting agent. Drysolid anionic or nonionic Wetters are preferred.

Dust formulations will normally contain from 5.0 weight percent to 25weight percent of active material,

27 from 0.005% to 1.0% Wetting agent, and from 3% to light grinding aiddiluent and the balance dense, rapid settling diluent. If made bydiluting a prepared wettable powder it will also contain a small amountof dispersing agent which has no active role when the composition isused as a dry dust.

(C) Emulsifiable liquids.Emulsifiable liquids are formulated bycombining the complexes of this invention with a suitable emulsifier andan organic liquid with low water solubility. The active component may becompletely dissolved in the organic liquid or it may be a finely groundsuspension in a nonsolvent liquid. Suitable organic liquids includealkylated naphthalenes, xylene, high-molecularweight ketones such asisophorones and dibutyl or diamyl ketone, esters such as amyl acetate,normalor isoparaffins and purified white oils. Most preferredemulsifiers are blends of oil-soluble sulfonates and nonionicpolyoxyethylene glycol esters or ethers of fatty acids or alkylatedphenols.

The active component in emulsifiable concentrates will be present atfrom 10 Weight percent to about 40 Weight percent. Combined emulsifierswill be present at from 3 weight percent to about 10 weight percent andthe balance will be an organic carrier liquid or solvent.

(D) Granules-Soil treatments with fungicides, either preorpost-emergence can frequently be most readily applied with granules.Granular products, with the complexes of this invention, can be made ina number of ways. The active materials can be dissolved in a volatilecarrier and sprayed upon preformed granules. They may be mixed aspowders with suitable diluents and binders, then moistened andgranulated followed by drying. Powders may also be applied to coarselyporous granules by tumbling together and applying some non-volatileliquid such as oil, glycol or a liquid nonionic surfactant to act as abinder. Rates of granule disintegration and dispersion of activematerial in moist soil can be controlled by choice of added surfactantsor selection of the binders used to form the granule.

Suitable preformed granules include those made from attapulgite clay,granular expanded vermiculite, ground corn cobs, ground nut shells orpreformed kaolinite granules. When active fungicide is placed upon suchcarriers the concentration may range from 1% to However, it is difficultto prevent segregation of active and carrier in concentration rangesabove about 10% on preformed granules. When higher concentrations ofactive are desired best results are obtained by premixing powderedactive, diluents, binders and surfactants then granulating so that theactive is distributed throughout the granule and not solely upon itssurface.

Suitable diluents for the preparation of granules by granulation orextrusion include kaolin clays, non-swelling Ca, Mg montmorillonites,and gypsum. Cohesion to a firm granule is usually obtained by moisteningcompacting and drying, with or without some binding agent. Kaolin claysform firm granules if bound together with gelatinous agents such asmethylcellulose, natural gums or swelling bentonite. Ca, Mg bentonitesrequire no binder, and gypsum can be made to form firm granules witheither the addition of plaster of Paris or certain salts such asammonium sulfate, potassium sulfate or urea which form double salts withgypsum.

The active content of formed granules can range from 190% although 75%active represents about the upper level if controlled disintegration ofthe granule in moist soil is desired. Control of disintegration rate isattained by controlled compaction, e.g. controlled extrusion pressure,and by the addition of inert water-soluble components such as sodiumsulfate which can leach away.

Such compositions can contain, in addition to the active ingredient ofthis invention, conventional insecticides, miticides, bactericides,nematocides, fungicides, of other agricultural chemicals such asfruit-set agents, fruit-thinning compounds, fertilizer ingredients andthe like, so that the compositions can serve useful purposes in additionto the control of fungi and mite infestations.

The following are illustrative of the agricultural chemicals that can beincluded in the compositions or, additionally, that may be added tosprays containing one or more of the active complexes.

1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-hexahydro-1,4-

endoexo-5,S-dimethanonaphthalene (aldrin)l,2,3,4,5,6-hexachlorocyclohexane (lindane)2,3,4,5,6,7,8,8-octachloro-4,7-methano-3a-4,7,7a-tetrahydroindane;

1, 1,1-trichloro-2,2-bis(p-chlorophenyl) ethane (DDT) 1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a-5,6,7,8,8a-octahydro-1,4-endo-exo-5,8-dimethanonaphthalene(dieldrin);

1,2,3,4,10,10-hexachloro6,7-epoxy-l,4,4a,5,6,7,8,8a-octahydro-1,4-endo-endo-5,6-dimethanonaphthalene(endrin);

1 (or 3a), 4,5,6,6,7,7-heptachloro-3a-4,7,7a-tetrahydro-4,7-methanoindene;

1, 1 1-trichloro-2,2-bis (p-methoxyphenyl) ethane (methoxychlor);

1,1-dichloro-2,2-bis(p-chlorophenyl) ethane;

chlgggiated camphene having a chlorine content of 67- 2-nitrol l-bis(p-chlorophenyl) butane;

1-naphthyl-N-methylcarbamate (Sevin methylcarbamic acid, ester withphenol, 4-(dimethylamino)-3,5-dimethyl;

methylcarbamic acid, ester with 1,3-dithiolan-2-oue oxime;

0,0-diethyl O-(2-isopropyl-4-methylpyrimid-6-yl) thiophosphate;

0,0-dimethyl 1-hydroxy-2,2,2-trichloroethyl phosphohate;

0,0-dimethyl S( 1,2-dicarbethoxyethyl) dithiophosphate (malathion)0,0-dimethyl O-p-nitrophenyl thiophosphate (methyl parathion);

0,0-dimethyl O-(3-chloro-4-nitrophenyl) thiophosphate;

0,0-diethyl O-p-nitrophenyl thiophosphate (parathion);

dl-2-cyclopentenyl-4-hydroxy-3-methyl-2-cyclopenten-lonechrysanthemumate;

0,0'- dimethyl-O-(2,2-dichlorovinyl) phosphate (DDVP); mixturecontaining 53.3% Bulan, 26.7% Prolan and 20.0% related complexes;

0,0tdimethyl O-(2,4,5-trichlorophenyl) phosphorothio- 0,0-dimethyl-S-(4-oxol ,2,3-benzotriazine-3- (4H)-ylmethyl) phosphorodithioate(Guthion);

bis (dimethylamino)phosphonous anhydride;

Qol-lditethyl O-(Z-keto-4-methyl-7-a-pyranyl) thiophos-O,O-diethyl(S-ethyl mercaptomethyl) dithiophosphate;

calcium arsenate;

sodium aluminofluoride;

dibasic lead arsenate;

2'-chloroethy1 l-methyl-Z-(p-tert-butylphenoxy)ethyl sulfite;

azobenzene;

ethyl 2-hydroxy-2,2-bis 4-chlorophenyl acetate;

0,0-diethyl O-[Z-(ethylmercapto)-ethyl] thiophosphate;

2,4-dinitro-6-sec-butylphenol;

toxaphene;

O-ethyl O-p-nitrophenylbenzenethiophosphonate;

4-chlorophenyl-4-chlorobenzenesulfonate;

p-chlorophenyl phenyl sulfone;

tetraethyl pyrophosphate;

1,1-bis(p-chlorophenyDethanol;

1,1-bis(chlorophenyl) -2,2,2-trichloroethanol;

p-chlorophenyl -p-chlorobenzyl sulfide;

bis (p-chlorophenoxy) methane;

3- 1-methyl-2-pyrrolidyl pyridine;

mixed ester of pyrethrolone and cinerolone keto-alcohols and twochrysanthemum acids;

cube and berris, both whole root and powdered;

ryanodine;

mixture of alkaloids known as veratrine;

dl-2-allyl-4-hydroxy-3-methyl-2-cyclopenten-l-one esterified with amixture of cis and trans dl-chrysanthemum monocarboxylic acids;

butoxypolypropylene glycol;

p-dichlorobenzene;

2-butoxy2'-thiocyanodiethyl ether;

naphthalene;

methyl O-carbamylthiolacetohydroxamate;

l,1-dichloro-2,2-bis (p-ethylphenyl)ethane;

methyl (methylcarbamyl) thiolacetohydroxamate;

p-dimethylaminobenzenediazo sodium sulfonate;

quinone oxya-minobenzooxohydrazone;

tetraalkyl thiuram disulfides such as tetramethyl thiuram disulfide ortetraethyl thiuram disulfide;

metal salts of ethylenebisdithiocarbamic acid, e.g. manganese, zinc,iron and sodium salts;

pentachloronitrobenzene;

n-dodecylguanidine acetate (dodine);

N-trichloromethylthiotetrahydrophthalimide (captan);

phenylmercury acetate;

2,4-dichloro-6-(o-chloroaniline)-s-triazine (Dyrene) N-methylmercuryp-toluenesulfonanilide;

chlorophenolmercury hydroxides;

nitrophenolmercury hydroxides;

ethylmercury acetate;

ethylmercury 2,3-dihydroxypropylmercaptide;

methylme'rcury acetate;

methylmercury 2,3-dihydroxypropylmercaptide;

3,3 ethylenebis(tetrahydro 4,6-dimethyl-2H-l,3,5-thi0- diazine-Z-thione)methylmercury dicyandiamide;

N-ethylmercury-p-toluenesulfonanilide;

1,4-dichloro-2,5-dimethoxybenzene;

metal (e.g. iron, sodium and zinc), ammonium and amine salts of dialkyldithiocarbamic acids;

tetrachloronitroanisole;

hexachlorobenzene;

hexachlorophene;

methylmercury nitrile';

tetrachloroquinine;

N-trichloromethylthiophthalimide;

1,2-dibromo-3-chloroprene;

1,2-dibromo-3-chloropropene;

dichloropropane-dichloropropene mixture;

ethylene dibromide;

chloropicrin;

sodium dimethyldithiocarbamate;

tetrachloroisophthalonitrile;

l-benzimidazolecarboxylic acid, 2-carboxyamino, dimethyl ester;

streptomycin;

2-(2,4,5-trichlorophenoxy) propionic acid;

p-chlorophenoxyacetic acid;

l-naphthaleneacetamide; and

N- 1-naphthyl)acetamide.

The agricultural chemicals listed above are merely exemplary of thecomplexes which can be mixed with the active complexes and are notintended to in any way limit the invention.

The use of pesticides such as those listed above in combination With acompound within the scope of this invention sometimes appears to greatlyenchance the activity of the active complex. In other words, anunexpected degree of activity is sometimes seen when another pesticideis used along with the active complex.

The complexes of the invention also have utility in that when they areadded to sewage, they result in an increase in the rate of sewagedecomposition. When added to soil, the' complexes increase the ratewhereby the nitrogen present in fertilizers is converted into usableplant food. The complexes also posses activity against the helminthparasites of warm blooded animals.

The complexes of the invention also have utility in 5 that they reducethe rate of degradation of chlorophyll and keep plants in an effectivephotosynthetic condition longer. The extension of the photosyntheticperiod or antisenescence activity results in increased yields of manygrains, fruits and vegetables. Also, the storage life is increased forgreen leafy vegetables, certain ornamental plant materials,green-chopped forage, and the like.

The utility of the complexes of the invention will be exemplified by thefollowing examples. All parts are parts by weight unless otherwiseindicated.

WETTABLE POWDERS Example 25 Percent l-(butylcarbamoyl)-2-benzimidazolecarbamic acid,

methyl ester, 2:1 complex with zinc, dihydrate 70 Dioctyl sodiumsulfosuccinate 4 Oleyl ester of sodium isethionate 3 Diatomaceous silica23 The above wettable powder is prepared by blending the componentstogether, then micropulverizing in a hammer mill, followed by airmilling to further reduce particle size.

The above composition is added to water in such an amount to provide 300p.p.m. of the active ingredient of invention. This preparation is thensprayed on alternate trees in an apple orchard in Virginia. The treesare known to have been infected with the apple scab pathogen two daysbefore the first treatment. There is also evidence of incipient powderymildew growth on a few of the leaves of each tree, and the overwinteringpopulation of spider mites are beginning to infest the orchard.

The spray is applied to fifteen-year-old apple trees at the rate of 50liters per tree at the pink stage of early bloom. Repeat sprays areapplied every three weeks during the spring and summer. At harvest timethe leaves on the sprayed trees are healthy and free of spider mites,and the fruit is full sized with good color and a smooth finish. Theuntreated trees, on the other hand, are heavily diseased with scab, andpowdery mildew and bronzed by a high population of spider mites. Thefruit on untreated trees is small and distorted with scab lesions. Thus,the composition of this invention, applied in the manner described,destroys both apple scab and powdery mildew inciting fungi and preventsa build up of spider mites, and therefore prevents disease and damage bythese organisms.

Any of the complexes described in Examples 2 through 24 can beformulated in the above manner and when applied will give similarresults.

Example 26 Percent 1 butylcarbamoyl 2 benzimidazolecarbamic acid,

methyl ester, 2:1 complex with manganese, di-

hydrate 5O Dodecylphenol condensate with 9 mols ethylene oxide 3 SodiumN-methyl, N-oleoyltaurate 1 Kaolin clay 46 Example 27 Percent lhexylcarbamoyl 2 benzimidazolecarbamic acid,

methyl ester, 2:1 complex with zinc, dihydrate 70 Sodium lauryl sulfate2 Sodium lignin sulfonate 2 Minus 270 mesh corn cob flour 26 The abovecomposition is blended, then pin milled until the active approaches anaverage particle size of about microns.

The above composition is added to water containing 300 p.p.m. of amodified phthalic glycerol alkyd resin surface active agent (Triton B1956) in an amount to provide 300 p.p.m. of the active complex of thisinvention. This aqueous preparation is sprayed at a rate of liters pertree on alternate trees in a peach orchard in North Carolina. Sprayingis started at the pink stage of bloom and repeated at 14 day intervalsuntil harvest time. The remaining trees in the planting are leftuntreated.

There are several warm wet periods during the blossom and early growingseason and fungus pathogens have a good opportunity to infect theblossoms and fruit. At the time of harvest the treated trees are healthyand the fruit is free of disease. The fruit on the untreated trees, onthe other hand, is badly rotted by the brown rot fungus and disfiguredwith peach scab.

Example 28 Percent l (p methoxybenzylcarbamoyl) 2 benzimidazolecarbamicacid, methyl ester, 2:1 complex with zinc, dihydrate 50 Diamyl sodiumsulfosuccinate 4 Dehydrated, partially desulfonated sodium ligninSulfonate 46 spot, powderly mildew, and infested wtih spider mites.

The same plants are sprayed every 7 days during the growing season andthe alternate plants are left unsprayed.

Two months after the treatments are initiated the treated roses arehealthy, growing vigorously and producing an abundance of blooms. Theuntreated bushes are, on the other hand, almost completely defoliated bydisease and supporting only a few small blossoms. The few remainingleaves were covered with mildew or injured by mites or black spotinfections.

All complexes of this invention can be formulated in the same way withsimilar results.

Example 29 Percent 1 (butylcarbamoyl) 2 benzimidazolecarbamic acid,methyl ester, 2:1 complex with manganese,

monohydrate 50 Dioctyl sodium sulfosuccinate 85% with Na benzoate(Aerosol OTB) 3 Low-viscosity methyl cellulose 0.75

' Cane sugar 46.25

The above components are blended and micropulverized, then air-filleduntil substantially all particles are 5 microns or less.

A uniform field planting of cantaloupe in North Carolina is inoculatedwith the powdery mildew fungus (Erysiphe cichoracearum). After 10 daysthis organism has become well established in the plants. At this timealternate rows are sprayed with water containing a suspension of thewettable powder prepared as described above. The concentration of thischemical suspension is such as to give 227 grams of the active compoundof this invention per 378 liters of water (0.06%). The spray is appliedat a volume of 1410 liters per hectare. The remaining rows are leftunsprayed.

After another 15 days the unsprayed rows are heavily damaged by powderymildew and some of the plants are dying. The sprayed rows, however, arehealthy and growing rapidly. The results indicate that the activecompound of the suspension acts as a curative fungicide.

Example 30 Percent l-(butylcarbamoyl) 2 benzimidazolecarbamic acid,

methyl ester, 2:1 complex with manganese 50 Sodium lauryl sulfate 2Nonylphenoxypoly(ethyleneoxy)ethanol (40 mols Pentaerythritol The abovecomposition is blended, then micropulverized, followed by air-milling tofurther reduce particle size until substantially all of the materialconsists of particles which are smaller than 5 microns as measured byAndersen pipette sedimentation.

Six field crates of oranges are picked from a commercial grove inFlorida. Three crates of oranges are dipped for three minutes in a waterbath containing a suspension made from the above formulation in anamount to give 300 parts per million by weight of the active ingredientof this invention. The remaining three crates are dipped in a similarfashion in water. All crates are set aside in a citrus storage house forthree weeks.

At the end of this time all fruit are examined. The fruit that has beendip-treated with the compound of this invention is still in goodcondition, but the fruit that is not so protected is largely rotted bythe blue mold fungus (Pcnicillium digitatum).

Example 31 Percent 1-( butylcarbamoyl) 2 benzimidazolecarbamic acid,

methyl ester, 2:1 complex with zinc 60 Alkylnaphthalenesulfonate, Nasalt 3 N-methyl-N-palmitoyltaurate, Na salt 2 Cane sugar 35 The abovecomponents are blended, micropulverized and air-milled to 5 micronparticle size or less, as determined by microscopic inspection ofaqueous dispersions of the formulation.

The above 50% wettable powder formulation is dispersed in water to givean active ingredient concentration of 3.6 grams per liter of water.Eight uniform apple trees of the same variety are selected for testing.Four of these are sprayed to run-off, which is approximately 2850 litersper hectare, at weekly intervals during the growing season with theabove formulation, and the other four trees are left unsprayed.

By the end of the season the unsprayed trees have developed very highpopulations of orchard mites and are highly infected with apple scab,Venturia inaequalis. Due to the feeding of the mites, the foliage isrusseted and drops prematurely. Also the untreated trees have poor twiggrowth and small, spotted fruit. The trees sprayed with the complex ofthis invention are essentially free of mites, their eggs and apple scab.As a result of the excellent mite control, the sprayed trees havefoliage of a thrifty, dark green color, and they exhibit good twiggrowth and fruit size.

GRANULES Example 32 Percent l-butylcarbamoyl 2 benzimidazolecarbamicacid,

methyl ester 2:1 complex with zinc, monohydrate 10Alkylnaphthalenesulfonic acid, sodium salt 1 Expanded vermiculitegranules 30-60 mesh 89 The active material and surfactant are taken upin acetone and sprayed upon the vermiculite with tumbling, followed byevaporation of the acetone.

A cucumber planting is established by dropping three cucumber seeds intoholes in the soil three centimeters deep and spaced one meter apart inthe row. Rows are 3 meters apart. Alternate rows are treated by placing2 grams of the granules described above into the planting holes.Adjacent rows are left untreated. Six weeks after planting, the plantsin the treated rows are completely healthy. The plants in the untreatedrows are heavily diseased with powdery mildew.

This demonstrates disease control by the active complex of thisinvention when picked up from the soil by roots and transportedsystemically into the foliage.

All complexes of this invention can be formulated in the same way withsimilar results.

Example 33 Percent l-(butylcarbamoyl) 2 benzimidazolecarbamic acid,

methyl ester, 2:1 complex with manganese l Dodecylphenol condensed with9 moles ethylene oxide Expanded 30-60 mesh vermiculite granules 85 Theactive component is first air-milled for minimum particle size, thenblended briefly with the vermiculite. The surfactant is then sprayedinto the blending mix and blending is continued for a few minutes. Thesurfactant acts as a binder to prevent segregation of powder and granuleand also aids rapid release when granules are placed in moist soil.

A field in California is seeded with cotton in the normal manner, exceptthat granules prepared as described above are added to alternate rows.These granules are dropped in such a way that some fall into the furrowand some are mixed with the covering soil. The rate of granuleapplication is such as to employ 0.45 kilogram of active chemical ofthis invention per 3600 linear meter of row. The remaining rows areuntreated.

Six weeks after planting many of the plants in the rows without thegranules are dead and other show soreshin lesions caused by Rhizoctoniasolani as well as heavy populations of the Pacific mite (Tetranychuspacificus). In the rows that had received the granules, all plantsremain alive and are healthy and free of mites. The effect on mites isclearly systemic.

WETTABLE POWDER Example 34 Percent l-(butylcarbamoyl) 2benzimidazolecarbamic acid,

methyl ester, 2:1 complex with zinc, dihydrate 50 Dioctyl sodiumsulfosuccinate 3 Sodium, N-methyl,N-palmitoyltaurate (Igepon TN 74) 4Sucrose 43 The above components are blended and pulverized, then airmilled until the particles are substantially all 5 microns or less.

A field planting of rice in Louisiana was infected with rice blast inthe early part of the growing season. Many older leaves are diseased andthe rice blast fungus is prescut to such an intensity that good cerealproduction is threatened. At the time of heading, when the rice flowersare in the boot, selected plots are sprayed.

The spray is an aqueous preparation containing the wettable powderdescribed above in an amount to provide 300 p.p.m. of the active complexand 500 p.p.m. of a modified phthalic glycerol alkyd resin surfaceactive agent (Triton B 1956). The spray is applied at a rate of 300liters per hectare. Two weeks later, as the rice is heading, a secondtreatment similar to the first is applied to the selected plots. Atharvest time, the rice in the treated plots is healthy with no neck rot.The untreated rice surrounding these plots, is heavily diseased, theheads have been broken off and most of the cereal lost due to attack byrice blast.

DUST

Example 35 Percent l octylcarbamoyl 2 benzimidazolecarbamic acid,

methyl ester, 2:1 complex with zinc, monohydrate l0 Diatomaceous silica10 Micaceous talc The active material and silica are first blendedtogether and milled, then mixed with the talc in a ribbon blender.

A grape vineyard is selected in California at a stage of developmentwhen the shoots are about 20 to 30 centimeters long. The older leaveshave active powdery mildew colonies on them. Individual plants aredusted with the above mentioned composition during a very calm period,early in the morning, when very little dust is blowing away to adjacentundusted vines. The rate of dust application is 2,000 gms. per acre. Thedust treatment is repeated in three weeks. At the time the grapes areripening, the treated vines have healthy leaves and fruit.

The nearby vines which were untreated have distorted shoots covered withpowdery mildew and the fruit is discolored and split due to severepowdery mildew infection.

EMULSIFIABLE OIL CONCENTRATE Example 36 Percent 1 trichloromethylthio 2benzimidazolecarbamic acid, methyl ester, 2:1 complex with zinc,dihydrate 25 White mineral oil 50-60 viscosity 70 Blend of oil solublesulfonates and polyoxyethylene ethers The above components are mixed andsand milled until the insoluble, active component is below 5 microns.The oil dispersion thus formed is emulsifiable in water.

One liter of the above composition is suspended in 1,000 liters ofwater. This preparation is then sprayed on apple trees at a rate of 40liters per tree. The trees are in the early stage of bloom (pink) andhave been subjected to a warm rain lasting two days and resulting inheavy infection by the apple scab fungus. The powdery mildew infectionsof the previous year were evident on some of the shoots and a few spidermites were active on the older leaves. Spray treatments are repeated attwo-week intervals until a month prior to harvest. Unsprayed apple treesadjacent to those receiving the above treatments show signs of diseaseby mid-season. Leaves spotted with apple scab begin to yell-ow and fall.Shoots stop growth and are dusty white with powdery mildew. Theuntreated trees become bronzed in color due to spider mite damage, andthe fruit is distorted by scab lesions.

The trees receiving regular treatments remain healthy and produce largeclean fruit of a good color and finish. Treatments are both curative andpreventative in their control of apple disease.

wherein Q is R is methyl or ethyl;

R is alkyl of 1 through 8 carbon atoms;

Me is zinc, copper, nickel, manganese, cobalt, cadmium,

iron, or chromium; and

nis0,1,1 /z or 2.

2. A complex of the formula of claim 1 which is 1- (butylcarbamoyl) 2benzimidazolecarbamic acid, methyl ester, 2:1 zinc complex, dihydrate.

3. A complex of the formula of claim 1 which is l- (butylcarbamoyl) 2benzimidazolecarbamic acid, methyl ester 2:1 zinc complex, monohydrate.

4. A complex of the formula of claim 1 which is 1- (butylcarbamoyl) 2benzimidazolecarbamic acid, methyl ester 2:1 zinc complex.

5. A complex of the formula of claim 1 which is l- (butylcarbamoyl) 2benzimidazolecarbamic acid, :methyl ester 2:1 manganese complex,dihydrate.

'6. A complex of the formula of claim 1 which is 1- (butylcarbamoyl) 2benzimidazolecarbamic acid, methyl ester, 2:1 manganese complex.

7. A complex of the formula of claim 1 which is l- (butylcarbamoyl) 2benzimidazolecarbamic acid, methyl ester 2:1 manganese complexmonohy-drate.

8. A process for making the complexes of claim 1 comprising preparing athree-phase system of:

(a) an aqueous solution of the acetate, chloride, sulfate, nitrate orcitrate of zinc, manganese, nickel, cobalt, copper, cadmium, iron orchromium;

(b) a water-immiscible organic solvent; and

36 (c) in said solvent a solid benzimidazolecarbamate of the formula:

wherein Q, X, R R R R.,, Z, D and E are as defined in claim 1;

agitating said three-phase system until the solid phase passes from theorganic phase to the aqueous phase; and recovering the resultingcomplex.

9. The process of claim 2 wherein the aqueous solution is zinc acetateor manganese acetate.

10. The process of claim 9 wherein the water-immiscible organic solventis ethyl acetate, amyl acetate or diethyl ether.

11. The process of claim 10 wherein the benzimidazolecarbamate isl-(butylcarbamoyl)-2-benzimidazolecarbamic acid, methyl ester.

12. A process for making the complexes of claim 1 com- 25 prising asystem of (a) a slurry of a solid benzimidazolecarbamate of the formula/N 0 oNHii-om X a Q agitating said system and recovering the resultingcomplex.

13. The process of claim 12 wherein an aqueous solution of the sulfateof zinc or manganese is used.

References Cited UNITED STATES PATENTS 2,933,504 4/1960 Klopping .Y260-299 ALEX MAZEL, Primary Examiner R. J. GALLAGHER, Assistant ExaminerUS. Cl. X.R.

mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 562,282 Dated February 9, 1971 Inventorfll) Hein L. Klopping It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

In Column 36 of the claims, at line 1 of Claim 9, "Claim 2" should read.Claim 8 and in Claim 12, line 2 between "comprising" and "8," insertpreparing Signed and sealed this 18th day of May 1971.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, Attesting OfficerCommissioner of Paten

